活性碳纤维负载铁酞菁的制备及催化性能的研究

发布时间：2017-12-27 09:34

本文关键词：活性碳纤维负载铁酞菁的制备及催化性能的研究　出处：《浙江理工大学》2017年硕士论文　论文类型：学位论文

【摘要】：水作为人类赖以生存的最重要的资源之一,在自然界中有着无可取代的地位,随着社会的发展,水资源的污染与安全问题越来越被人们广泛关注。工业废水是水污染的最大污染源,如共轭染料、氯代芳香族化合物、抗生素等。近年来,抗生素类污染物作为一种新型污染物不断排入水体并且在水体中持续存在,对水生态环境以及人类健康造成了威胁。化学和生物等降解技术引起广泛关注,其中高级氧化技术(AOPS)由于其具有适用范围广、反应速率快、氧化能力强等特点,被成功应用到自然水体和污水中抗生素等多种有机污染物的降解。因抗生素独特的性质,一般的方法很难将其降解,其在环境中大量累积会造成微生物生态平衡的破坏,如果人们将其摄入体内很有可能会诱使人体产生耐药性,影响对一些疾病的治疗。基于本课题组以前的研究成果,开发一种高效绿色去除废水中有机污染物的催化体系具有重要意义。高级氧化技术(AOPs)基于自由基,羟基自由基(·OH)和硫酸根自由基(SO4·-)的形成和其他自由基氧化方法,与传统氧化剂相比,中间自由基具有非常强的活性,选择性较低,其标准氧化电位较高,可有效氧化难处理的抗生素污染物。对于不同的目标污染物,需要选择最适合的氧化剂,不同的氧化剂对应着不同的氧化机理及路线。金属酞菁结构和细胞色素P-450活性中心金属卟啉结构相似,使用不同载体负载或不同氧化剂活化,可制备各种不同功能催化系统。活性碳纤维具有独特的物理吸附性质和多孔结构、良好的电化学性质,常被作为各种催化剂载体应用于多个领域。本文利用两种不同的键合方法,分别使用脱氨基法和酰胺化方法改性活性碳纤维得到不同的负载型金属酞菁催化剂(ACFs-FeTNPc,ACFs-CONH-FeTNPc)。采用UV-vis、XPS、FTIR等方法对催化剂进行表征结果表明FeMATNPc成功地通过键合方式负载到活性碳纤维上。选用磺胺甲恶唑(SMX)和酸性红(AR1)作为目标污染物,H_2O_2及PMS为氧化剂,研究催化剂的催化氧化能力。实验结果表明:ACFs-FeTNPc/H_2O_2体系在中性条件下与Fe TNPc/H_2O_2相比具有较高的活性,说明ACF作为载体的引入可以极大地改善催化体系的活性;ACFs-CONH-FeTNPc/PMS体系相较于ACFs-CONH-FeTNPc/H_2O_2体系,对酸性红AR1的催化活性大大的提高,且其催化效率也大于FeTNPc/H_2O_2体系。EPR测试两个催化体系分别有羟基自由基(·OH)和过硫酸根自由基(SO4·-)的存在,ACFs-FeTNPc/H_2O_2反应是一个羟基自由基为主导的反应,并伴有一定的高价机理。ACFs-CONH-FeTNPc/H_2O_2反应也是羟基自由基为主导,硫酸根自由基为辅的反应。本论文的研究提供了一种通过共价键合的方法制备合成负载型催化剂,通过选择不同的氧化剂形成不同的催化体系,为催化体系的优化设计奠定了一定的基础。
[Abstract]:As one of the most important resources for human survival, water plays an indispensable role in nature. With the development of society, the pollution and safety of water resources is attracting more and more attention. Industrial wastewater is the biggest pollution source of water pollution, such as conjugated dyes, chlorinated aromatic compounds, antibiotics and so on. In recent years, as a new pollutant, antibiotic pollutants are continuously discharged into the water body and continue to exist in water, which poses a threat to the water environment and human health. Chemical and biological degradation technologies have attracted wide attention. Advanced oxidation technology (AOPS) has been applied to the degradation of various organic pollutants such as antibiotics in natural waters and sewage because of its wide application scope, fast reaction speed and strong oxidizing ability. Because of the unique nature of antibiotics, the general method is difficult to degrade, and its accumulation in the environment will cause the destruction of microbial ecological balance. If people ingested the body, it may lead to the resistance of human body to some diseases. Based on the previous research results of this group, it is of great significance to develop a highly efficient green catalytic system for removing organic pollutants from wastewater. Advanced oxidation technology (AOPs) based on free radical, hydroxyl radical (- OH) and sulfate radical (SO4 -) formation and other free radical oxidation method, compared with the traditional oxidation agent, intermediate free radical has very strong activity and low selectivity, the standard high oxidation potential, effective oxidation refractory antibiotic. For different target pollutants, it is necessary to choose the most suitable oxidant. Different oxidants correspond to different oxidation mechanisms and routes. The structure of metalloporphyrins is similar to that of cytochrome P-450 active center metalloporphyrins. Various functional catalytic systems can be prepared by activating different carriers or activating oxidants. Active carbon fiber (CF) has unique physical adsorption properties, porous structure and good electrochemical properties. It is often used as a catalyst carrier in many fields. In this paper, two different bonding methods were used to modify the activated carbon fibers by deamination and amidation respectively, and different supported metallo phthalocyanine catalysts (ACFs-FeTNPc, ACFs-CONH-FeTNPc) were obtained. UV-vis, XPS, FTIR and other methods were used to characterize the catalyst. The results showed that FeMATNPc was loaded on the activated carbon fiber successfully by bonding. Sulfamethoxazole (SMX) and acid red (AR1) were selected as the target pollutants, and H_2O_2 and PMS were used as oxidants to study the catalytic oxidation capacity of the catalyst. The experimental results show that ACFs-FeTNPc/H_2O_2 system has higher activity compared with Fe TNPc/H_2O_2 under neutral condition, ACF as the carrier of the introduction of the system can greatly improve the catalytic activity; ACFs-CONH-FeTNPc/PMS system compared to the ACFs-CONH-FeTNPc/H_2O_2 system, the catalytic activity of acid red AR1 is greatly improved, and the catalytic efficiency is higher than FeTNPc/H_2O_2 system. EPR test the existence of hydroxyl radical (? OH) and persulfate radical (SO4? -) in the two catalytic systems. ACFs-FeTNPc/H_2O_2 reaction is a hydroxyl radical dominated reaction, accompanied by a high price mechanism. The ACFs-CONH-FeTNPc/H_2O_2 reaction is also the reaction that the hydroxyl radical is dominant and the radical radical is supplemented by the sulfate radical. This research provides a way to prepare supported catalysts by covalent bonding, and form different catalytic systems by selecting different oxidants, thus laying a solid foundation for the optimization design of catalytic system.
【学位授予单位】：浙江理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：X703

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