基于摩擦纳米发电机的自驱动电化学系统在有机污染物处理中的研究

发布时间：2018-04-21 06:51

本文选题：摩擦纳米发电机 + 自驱动　；参考：《河南师范大学》2017年硕士论文

【摘要】：有机污染物对生物体和环境具有极大的危害性,预防、控制和治理有机物污染已成为当前备受关注的问题。电化学法作为一种理想的处理废水有机污染物的方法,可以在短时间内将毒性大、难降解的有机污染物处理成无毒或无二次污染的完全降解物。然而,传统的电化学降解装置靠外部能源驱动,外部能源主要来自煤、石油等化石燃料,这无疑在加重能源负担的同时,造成了新的环境污染,也极大限制了电化学降解在污染物处理中的广泛应用。摩擦纳米发电机(Triboelectric Nanogenerator,TENG)是一种基于摩擦带电和静电感应原理的新型能源转化装置,能将环境中种类繁多的闲散、无用、甚至影响人类生活的机械能转换成电能,相对于传统的发电机,具有质量轻、体积小、选材广、造价低等优点。将TENG和电化学有机污染物处理装置相结合,组成自驱动电化学降解系统,借助水流、风能、人体运动等自然界中纷繁复杂的机械振动驱动TENG工作,不仅能够实现环境中机械能的收集利用,而且能够在一定程度上解决低浓度有机物污染的问题。因此,基于TENG的自驱动电化学装置在废水有机物处理中具有广阔的应用前景。本论文基于摩擦纳米发电机的自驱动电化学系统在有机污染物处理中的应用展开研究。主要完成以下三个目标:(1).设计构建输出效率高、廉价、易于调控的TENG;(2).基于设计的TENG开展自驱动电化学系统在有机污染物处理中的应用;(3).深入研究相关有机污染物的消除过程和消除机理。基于上述目标,我们完成了如下研究工作:(1)设计出交叉折叠结构的新型摩擦纳米发电机(PICL-TENG),并首次将自驱动电化学系统应用于苯胺类有机物的氧化聚合。通过螺丝和弹簧将多个摩擦单元铰接,成功制作出基于平面滑动模式的新型交叉折叠结构的TENG。随后,借助高压电荷注入技术增加摩擦层表面电荷密度,有效提升了PICL-TENG的输出性能,使其开路电压、短路电流和峰功率密度分别达到845.6 V、69.9μA和1.59 W m-2。选取苯胺、N-羟乙基苯胺、三(4-溴苯)胺这三种具有不同取代基的苯胺类有机物作为研究对象,依靠PICL-TENG供能,成功使苯胺类有机物发生电化学氧化。同时,研究结果表明,PICL-TENG作为供能系统,在任何季节均能实现苯胺类有机物的氧化,进而拓展了自驱动电化学体系的应用范围。(2)构建出多层联动结构的新型摩擦纳米发电机(PMLL-TENG),并成功应用于自驱动甲基黄染料的电化学氧化降解。借助连杆和螺丝将多个摩擦单元并联,制作成多个摩擦层可以同时接触和分离的多层联动结构的TENG。通过对PTFE膜进行电荷注入处理,其平均开路电压、短路电流和峰功率密度分别提升至793 V、0.56 mA和30.8 W m-2。在PMLL-TENG驱动的电化学体系中,高毒性的甲基黄染料最终完全降解为二氧化碳。此外,以循环伏安、气相色谱-质谱联用和核磁共振氢谱等技术为研究手段,对其氧化过程和机理进行探究,初步探索出甲基黄的降解是通过阳极界面处产生的活性氧如HO·,攻击与-N=N-相邻的C-N键,最终间接氧化降解为CO2。(3)制作出旋转圆盘结构的摩擦纳米发电机(rd-TENG),并成功用于4-氨基偶氮苯的自驱动电化学氧化降解或聚合。首次使用铝塑板做电极和基底,通过对铝塑板和亚克力板进行雕刻处理,制作出具有精美图案的定子和转子,进而组装成旋转圆盘结构的TENG。用电动装置模拟自然界中的机械能,研究出转速和rd-TENG输出性能的关系。利用rd-TENG输出的电能,4-氨基偶氮苯可以选择性氧化为聚合物或二氧化碳。通过分析不同电压区间和扫速的循环伏安图像,结合交流阻抗、气相色谱-质谱联用、紫外吸收光谱等技术,分析4-氨基偶氮苯的降解/聚合过程:在低电压下,4-氨基偶氮苯聚合成低聚物;在高电压下,通过阳极界面产生的活性物如HOCl/Cl2快速攻击-N=N-邻位的C-N,并在-NH2的邻位亲核取代苯环上的氢,HOCl/Cl2进一步氧化生成的中间物直至降解为CO2。据此,可以通过合理控制电化学氧化电位对AAB进行降解或聚合,这对有机污染物的处理具有指导意义。
[Abstract]:Organic pollutants have great harm to organisms and the environment. Prevention, control and control of organic pollutants have become an issue of great concern. As an ideal method of treating organic pollutants in wastewater, electrochemical method can treat organic pollutants with large toxic and difficult degradation into non-toxic or no two pollution in a short time. However, the traditional electrochemical degradation device is driven by external energy, and the external energy is mainly from coal, petroleum and other fossil fuels, which undoubtedly aggravates the energy burden, resulting in new environmental pollution, and it also greatly restricts the extensive application of electrochemical degradation in the treatment of pollutants. Triboelectr IC Nanogenerator, TENG) is a new type of energy conversion device based on the principle of friction electrification and electrostatic induction. It can convert a wide variety of idle, useless, and even influence the mechanical energy of human life into electrical energy. Compared with the traditional generator, it has the advantages of light quality, small size, wide selection of materials and low cost. The machine pollutant treatment device combines the self driving electrochemical degradation system to drive TENG with the help of the complicated mechanical vibration in nature, such as water flow, wind energy, human body movement and so on. It can not only realize the collection and utilization of mechanical energy in the environment, but also solve the problem of low concentration organic matter to a certain extent. Therefore, based on TE NG's self driven electrochemical device has a broad application prospect in the treatment of wastewater organic matter. This paper is based on the application of the self driven electrochemical system of friction nanoscale in the treatment of organic pollutants. The following three objectives are completed: (1). The design and construction of high efficiency, cheap, easy to regulate and control of TENG; (2). TENG is used to carry out the application of self driven electrochemical system in the treatment of organic pollutants; (3) in-depth study of the elimination process and elimination mechanism of related organic pollutants. Based on the above objectives, we have completed the following research work: (1) a new type of friction nanoscale generator (PICL-TENG) is designed for the first time, and the self driven electrification is the first time. The system is applied to the oxidation polymerization of aniline organic matter. A number of friction units are hinged by screws and springs. A new type of cross folded structure TENG. based on plane sliding mode is successfully produced. The charge density of the surface of the friction layer is increased by the high pressure charge injection technology, which can improve the output performance of PICL-TENG and make it open. Voltage, short circuit current and peak power density reach 845.6 V, 69.9 mu A and 1.59 W m-2. to select aniline, N- hydroxyethyl aniline, three (4- bromine) amine, which have different substituents of aniline as the research object, and rely on PICL-TENG to supply energy, the aniline type machine can be electrochemical oxidation. At the same time, the results show PICL-TE NG, as an energy supply system, can realize the oxidation of aniline like organic matter in any season, and then expand the application scope of the self driven electrochemical system. (2) a new type of friction nanoscale generator (PMLL-TENG) is constructed and applied to the electrochemical oxidation degradation of self driving methyl yellow dye. The friction unit is connected in parallel, and TENG. is injected into the PTFE film by the multi-layer linkage with multiple friction layers. The average open circuit voltage, short circuit current and peak power density are increased to 793 V, 0.56 mA and 30.8 W m-2. in PMLL-TENG driven electrochemical system, with high toxic methyl yellow. The dye finally completely degraded to carbon dioxide. In addition, the oxidation process and mechanism were explored by cyclic voltammetry, gas chromatography mass spectrometry combined with nuclear magnetic resonance spectroscopy. The degradation of methyl yellow was preliminarily explored as the active oxygen, such as HO, produced by the anode interface, attacking the C-N bonds adjacent to -N=N-, and ultimately indirectly. The friction nanoscale generator (rd-TENG) was produced by the oxidation degradation of CO2. (3), and it was successfully used for the self driven electrochemical oxidation degradation or polymerization of 4- amino azobenzene. The aluminum plastic plate was first used as the electrode and substrate. The stators and rotors with fine patterns were made by engraving the aluminum plastic plate and acrylic plate. The TENG., which is assembled into a rotating disk structure, simulates the mechanical energy in nature with an electric device, and studies the relationship between the rotational speed and the output performance of the rd-TENG. The 4- amino azobenzene can be selectively oxidized to polymer or carbon dioxide by using the output of rd-TENG. Impedance, gas chromatography-mass spectrometry (GC-MS), UV absorption spectroscopy and other techniques to analyze the degradation / polymerization process of 4- amino azobenzene: at low voltage, 4- amino azobenzene is polymerized into oligomers; at high voltage, the active substances produced by the anode interface, such as HOCl/Cl2, quickly attack the C-N of the -N=N- neighborhood, and replace the hydrogen on the benzene ring in the neighborhood of the -NH2. HOCl/Cl2 can be further oxidized and degraded into CO2., and the AAB can be degraded or polymerized by reasonable control of electrochemical oxidation potential, which is of guiding significance for the treatment of organic pollutants.

【学位授予单位】：河南师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：X703;O646

【参考文献】