催化活化氧气产生高活性自由基体系的构建及其效能研究
发布时间：2019-06-15 04:52
【摘要】：基于活化氧气的高级氧化技术作为一种简单、绿色、低成本的处理技术,在水处理领域中已引起广泛的关注,高级氧化技术中产生的活性自由基是作用于水中污染物氧化和降解的关键物种,因此,在温和条件下,活化氧气产生高活性自由基简单、高效、低成本体系的构建具有较强的科学意义和实际应用价值。本研究构建了基于邻氨基酚、对氨基酚和对苯二酚类还原性有机污染物的“还原性物质/Co2+-HCO3-”催化活化氧气产生高活性自由基的体系,分别从催化活化氧气体系的构建、底物的氧化降解特性、产生活性物种的类型、机制以及体系的效能研究等方面进行了系统详细的探讨,得出一些创新性结论。①本研究成功构建了基于邻氨基酚(OAP)、对氨基酚(PAP)和对苯二酚(H2Q)的“还原性物质/Co2+-HCO3-”催化活化氧气氧化产生高活性自由基的体系,该体系表现出了较好的催化氧化活性,还原性物质自身对于活性自由基的产生起着非常重要的作用,进一步对构建体系的效能研究表明,所构建的PAP-Co2+-HCO3-和H2Q-Co2+-HCO3-体系在氧化自身还原性物质的同时对于含染料废水的处理也表现出一定活性,在废水处理过程中能达到以废治废的目的。②OAP-Co2+-HCO3-体系中,OAP能被有效地氧化为2-氨基吩恶嗪-3-酮(APZ),体系中Co2+、HCO3-和O2对OAP的氧化过程缺一不可;O2与形成的Co II(HCO3-)(OAP)配合物相互作用,生成O2?-(单电子还原产物)和O22-(双电子还原产物),O22-经过歧化作用和质子化作用生成中间产物H2O2;电子顺磁共振技术和自由基抑制技术研究表明体系中生成的H2O2分解成的非游离型羟基自由基?OH是作用于OAP氧化的活性物种。③PAP-HCO3-和PAP-Co2+-HCO3-体系均能活化氧气作用于PAP的氧化,Co2+的加入能够促进在PAP-Co2+-HCO3-体系产生非游离型羟基自由基,该非游离型羟基自由基是作用于PAP氧化的主要活性物种,它的产生来自于两个步骤:i)O2的还原产物O2-?介导的H2O2的生成,ii)生成的H2O2与Co2+-HCO3-配合物通过Fenton反应生成非游离型羟基自由基,与此同时,在PAP氧化过程中产生的高活性?OH自由基能进一步作用于偶氮染料AOII的脱色降解。④H2Q-HCO3-和H2Q-Co2+-HCO3-体系均能活化氧气作用于H2Q的氧化,在HCO3-溶液中,H2Q的氧化过程为,首先失去一个电子转化为半醌自由基BQ?-,继而再失去一个电子转化为对苯醌,在此过程中O2被还原成H2O2,在Co2+的作用下H2O2分解成羟基自由基,并证明体系中产生羟基自由基是作用于H2Q的主要活性物种,另外体系中的产生HCO4-也部分作用于H2Q的氧。H2Q-Co2+-HCO3-体系能作用于AOII的降解,体系中产生的羟基自由基能有效攻击AOII分子结构上的两个C-N键,AOII分子结构中的N元素以N2的形式释放出去,体系中检测到的AOII的降解产物主要为对苯磺酸钠和1,2-萘醌及其进一步氧化产物。
[Abstract]:As a simple, green and low cost treatment technology, advanced oxidation technology based on activated oxygen has attracted extensive attention in the field of water treatment. The active free radicals produced in advanced oxidation technology are the key species acting on the oxidation and degradation of pollutants in water. Therefore, under mild conditions, activated oxygen produces high active free radicals. The construction of low cost system has strong scientific significance and practical application value. In this study, a "reductive substance / Co2-HCO3-" catalyzed activated oxygen to produce highly active free radicals based on o-aminophenol, p-aminophenol and hydrocatechol reductive organic pollutants was constructed. The construction of catalytic activated oxygen system, the oxidative degradation characteristics of substrate, the type of active species produced, the mechanism and the efficiency of the system were discussed in detail. Some innovative conclusions are drawn. 1 in this study, a system based on o-aminophenol (OAP), p-aminophenol (PAP) and hydrocatechol (H2Q) was successfully constructed, which catalyzed the oxidation of activated oxygen to produce highly active free radicals. The system showed good catalytic oxidation activity, and the reductive substances themselves played a very important role in the production of active free radicals. The further study on the efficiency of the construction system shows that the constructed PAP-Co2-HCO3- and H2Q-Co2-HCO3- systems not only oxidize their own reductive substances, but also show certain activity for the treatment of dye-containing wastewater, and can achieve the purpose of treating waste with waste in the process of wastewater treatment. In 2OAP-Co2-HCO3- system, OAP can be effectively oxidized to Co2 in 2-aminophene oxazin-3-one (APZ), system. The oxidation process of OAP by HCO3- and O2 is indispensable. O _ 2 interacts with the formed Co II (HCO3-) (OAP) complex to form O _ 2 (single electron reduction product) and O22-(double electron reduction product). O _ 22-forms intermediate H _ 2O _ 2 through disambiguation and protonation. Electron parammagnetic resonance technique and free radical inhibition technique show that the non-free hydroxyl radical formed by H2O2 in the system? OH is an active species acting on the oxidation of OAP. 3PAP-HCO3- and PAP-Co2-HCO3- systems can activate oxygen to act on the oxidation of PAP, and the addition of Co2 can promote the production of non-free hydroxyl radicals in PAP-Co2-HCO3- system. The non-free hydroxyl radical is the main active species acting on PAP oxidation, and its production comes from the reduction product O2 of: i) O2 in two steps. The H2O2 formed by, ii) mediated by H2O2 reacts with Co2-HCO3- to form non-free hydroxyl radical by Fenton reaction. At the same time, the high activity OH radical produced during PAP oxidation can further act on the decolorization and degradation of azo dye AOII. 4H2Q-HCO3- and H2Q-Co2-HCO3- systems can activate oxygen to oxidize H2Q. In HCO3- solution, the oxidation process of H2Q is. In this process, O2 is reduced to H2O2, and H2O2 is decomposed into hydroxyl radical under the action of Co2. It is proved that the hydroxyl radical in the system is the main active species acting on H2Q, and the production of HCO4- in the system can also partly act on the oxygen of H2Q. The H2Q-Co2-HCO3- system can act on the degradation of AOII, and it is proved that the hydroxyl radical produced in the system is the main active species acting on H2Q. in addition, the generation of hydroxyl radical in the system can also partly act on the oxygen of H2Q. H2Q-Co2-HCO3- system can act on the degradation of AOII. The hydroxyl radical produced in the system can effectively attack two C-N bonds on the molecular structure of AOII. The N element in the molecular structure of AOII is released in the form of N2. The degradation products of AOII detected in the system are mainly sodium p-benzenesulfonate and 1, 2-Naphthoquinones and their further oxidation products.
【学位授予单位】：武汉纺织大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：X703.1
[Abstract]:As a simple, green and low cost treatment technology, advanced oxidation technology based on activated oxygen has attracted extensive attention in the field of water treatment. The active free radicals produced in advanced oxidation technology are the key species acting on the oxidation and degradation of pollutants in water. Therefore, under mild conditions, activated oxygen produces high active free radicals. The construction of low cost system has strong scientific significance and practical application value. In this study, a "reductive substance / Co2-HCO3-" catalyzed activated oxygen to produce highly active free radicals based on o-aminophenol, p-aminophenol and hydrocatechol reductive organic pollutants was constructed. The construction of catalytic activated oxygen system, the oxidative degradation characteristics of substrate, the type of active species produced, the mechanism and the efficiency of the system were discussed in detail. Some innovative conclusions are drawn. 1 in this study, a system based on o-aminophenol (OAP), p-aminophenol (PAP) and hydrocatechol (H2Q) was successfully constructed, which catalyzed the oxidation of activated oxygen to produce highly active free radicals. The system showed good catalytic oxidation activity, and the reductive substances themselves played a very important role in the production of active free radicals. The further study on the efficiency of the construction system shows that the constructed PAP-Co2-HCO3- and H2Q-Co2-HCO3- systems not only oxidize their own reductive substances, but also show certain activity for the treatment of dye-containing wastewater, and can achieve the purpose of treating waste with waste in the process of wastewater treatment. In 2OAP-Co2-HCO3- system, OAP can be effectively oxidized to Co2 in 2-aminophene oxazin-3-one (APZ), system. The oxidation process of OAP by HCO3- and O2 is indispensable. O _ 2 interacts with the formed Co II (HCO3-) (OAP) complex to form O _ 2 (single electron reduction product) and O22-(double electron reduction product). O _ 22-forms intermediate H _ 2O _ 2 through disambiguation and protonation. Electron parammagnetic resonance technique and free radical inhibition technique show that the non-free hydroxyl radical formed by H2O2 in the system? OH is an active species acting on the oxidation of OAP. 3PAP-HCO3- and PAP-Co2-HCO3- systems can activate oxygen to act on the oxidation of PAP, and the addition of Co2 can promote the production of non-free hydroxyl radicals in PAP-Co2-HCO3- system. The non-free hydroxyl radical is the main active species acting on PAP oxidation, and its production comes from the reduction product O2 of: i) O2 in two steps. The H2O2 formed by, ii) mediated by H2O2 reacts with Co2-HCO3- to form non-free hydroxyl radical by Fenton reaction. At the same time, the high activity OH radical produced during PAP oxidation can further act on the decolorization and degradation of azo dye AOII. 4H2Q-HCO3- and H2Q-Co2-HCO3- systems can activate oxygen to oxidize H2Q. In HCO3- solution, the oxidation process of H2Q is. In this process, O2 is reduced to H2O2, and H2O2 is decomposed into hydroxyl radical under the action of Co2. It is proved that the hydroxyl radical in the system is the main active species acting on H2Q, and the production of HCO4- in the system can also partly act on the oxygen of H2Q. The H2Q-Co2-HCO3- system can act on the degradation of AOII, and it is proved that the hydroxyl radical produced in the system is the main active species acting on H2Q. in addition, the generation of hydroxyl radical in the system can also partly act on the oxygen of H2Q. H2Q-Co2-HCO3- system can act on the degradation of AOII. The hydroxyl radical produced in the system can effectively attack two C-N bonds on the molecular structure of AOII. The N element in the molecular structure of AOII is released in the form of N2. The degradation products of AOII detected in the system are mainly sodium p-benzenesulfonate and 1, 2-Naphthoquinones and their further oxidation products.
【学位授予单位】：武汉纺织大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：X703.1
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