基于电纺丝技术的一维功能性纳米材料的研制
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摘要
一维纳米材料因其具有巨大的比表面积和量子效应,比传统材料具有更好的光电、磁学、催化、传感等性质。在纳米光电器件、传感器、纳米生物技术、能量存储及转换等领域具有极其重要的作用。近年来,有关一维功能纳米材料的研究受到了越来越多的关注,各种制备方法不断涌现。在众多的制备方法中,高压静电纺丝技术不仅具有成本低、方法简单易行、可大量生产等优势,更重要的是应用范围非常广泛,对材料的要求比较低,而且所得的纤维均匀、连续、直径可控、长度可达到宏观尺度。
本论文以高压静电纺丝技术为基础,结合溶胶-凝胶技术和模板技术,成功的制备了分别具有催化、电化学、光电、湿度传感等功能的一维纳米材料,并对其相应的性质进行了表征。主要包括以下四部分工作:第一,在高强度的聚丙烯腈纤维内部负载贵金属纳米粒子,选择了催化还原对硝基苯酚的实验作为催化模型,对贵金属负载量、催化效率、循环再生、催化剂残留量等问题进行了研究。第二,通过电纺丝纤维模板法制备了纯的聚苯胺纤维、高分子/聚苯胺核壳纤维以及内部负载银纳米粒子的聚苯胺纳米长管,所得的聚苯胺一维纳米材料具有很好的导电性能,在中性条件下仍具有良好的电化学活性。第三,利用电纺丝法结合表面气固反应技术制备硫化亚铜量子敏化二氧化钛纳米纤维,这些纤维具有很好的光电性能,其光学响应范围扩大至整个可见光区。第四,通过电纺丝纤维模板法制备了碱金属盐掺杂的二氧化钛纳米长管,这些纳米长管具有非常优异的湿敏传感性能。
Nanomaterials have unique electronic, photonic, magnetic and catalytic properties due to their large surface and quantum effect. In recent years, one dimensional(1D) nanostructure materials have been intensive researched and a large number of synthetic and fabrication methods have already been demonstrated for generating 1D nanostructures in the form of fibers, wires and tubes from various materials. Among these methods, electrospinning seems to provide the simplest approach to nanofibers (nanowire or nanotube) that are exceptionally long in length, uniform in diameter, and diversified in composition.
In this dissertation, we have fabricated a series of functional nanofibers based on electrospinning and template technique.
1) Noble metal nanoparticles dispersed in polyacrylonitrile nanofiber film were prepared via electrospinning and the catalytic activities for reduction of p-nitrophenol were investigated. The results showed that the nanofiber mats had very excellent catalytic activity and they could be easily seperated from the solution and reused for more than 30 times with very little catalytic activity loss. Besides, the remanet of noble metal nanoparticles in the reaction system was very little.
2) We have successfully prepared polyaniline nanofibers, polyaniline/other polymers core-shell fibers and polyaniline nanotubes with silver nanoparticles incapsulated by using electrospinning UTFE method. All the polyaniline fibers above showed very good conductivity and especially the polyaniline/Ag nanotubes have a range-expanded electroactivity of pH= 0-7.
3) We prepared Cu2S-Doped TiO2 nanofibers by elelctrospinning and gas-solid reaction. The dispersion of Cu2S nanoparticles in polymer fibers are studied and the results showed that the Cu2S nanoparticles is uniform and well dispersed in TiO2 fibers. We studied the formation of Cu2S nanoparticles in the TiO2 fibers and their photoelectricity properties. The Cu2S-Doped TiO2 nanofibers were stable and the SPS results showed that the TiO2 fibers’s light response extended from the UV light area to the whole visible light area.
4) We have fabricated and investigated a highly sensitive and stable humidity nanosensor based on alkali metal salts-doped TiO2 nanofibers through electrospinning and calcination techniques. The sensor exhibited excellent characteristics including ultrafast response and recovery behavior, good reproducibility, linearity, and stability. All these characteristics above are very important in humidity detection and control. Moreover, our method provided a useful platform to design and construct highly effective humidity nanodetectors.
本论文以高压静电纺丝技术为基础,结合溶胶-凝胶技术和模板技术,成功的制备了分别具有催化、电化学、光电、湿度传感等功能的一维纳米材料,并对其相应的性质进行了表征。主要包括以下四部分工作:第一,在高强度的聚丙烯腈纤维内部负载贵金属纳米粒子,选择了催化还原对硝基苯酚的实验作为催化模型,对贵金属负载量、催化效率、循环再生、催化剂残留量等问题进行了研究。第二,通过电纺丝纤维模板法制备了纯的聚苯胺纤维、高分子/聚苯胺核壳纤维以及内部负载银纳米粒子的聚苯胺纳米长管,所得的聚苯胺一维纳米材料具有很好的导电性能,在中性条件下仍具有良好的电化学活性。第三,利用电纺丝法结合表面气固反应技术制备硫化亚铜量子敏化二氧化钛纳米纤维,这些纤维具有很好的光电性能,其光学响应范围扩大至整个可见光区。第四,通过电纺丝纤维模板法制备了碱金属盐掺杂的二氧化钛纳米长管,这些纳米长管具有非常优异的湿敏传感性能。
Nanomaterials have unique electronic, photonic, magnetic and catalytic properties due to their large surface and quantum effect. In recent years, one dimensional(1D) nanostructure materials have been intensive researched and a large number of synthetic and fabrication methods have already been demonstrated for generating 1D nanostructures in the form of fibers, wires and tubes from various materials. Among these methods, electrospinning seems to provide the simplest approach to nanofibers (nanowire or nanotube) that are exceptionally long in length, uniform in diameter, and diversified in composition.
In this dissertation, we have fabricated a series of functional nanofibers based on electrospinning and template technique.
1) Noble metal nanoparticles dispersed in polyacrylonitrile nanofiber film were prepared via electrospinning and the catalytic activities for reduction of p-nitrophenol were investigated. The results showed that the nanofiber mats had very excellent catalytic activity and they could be easily seperated from the solution and reused for more than 30 times with very little catalytic activity loss. Besides, the remanet of noble metal nanoparticles in the reaction system was very little.
2) We have successfully prepared polyaniline nanofibers, polyaniline/other polymers core-shell fibers and polyaniline nanotubes with silver nanoparticles incapsulated by using electrospinning UTFE method. All the polyaniline fibers above showed very good conductivity and especially the polyaniline/Ag nanotubes have a range-expanded electroactivity of pH= 0-7.
3) We prepared Cu2S-Doped TiO2 nanofibers by elelctrospinning and gas-solid reaction. The dispersion of Cu2S nanoparticles in polymer fibers are studied and the results showed that the Cu2S nanoparticles is uniform and well dispersed in TiO2 fibers. We studied the formation of Cu2S nanoparticles in the TiO2 fibers and their photoelectricity properties. The Cu2S-Doped TiO2 nanofibers were stable and the SPS results showed that the TiO2 fibers’s light response extended from the UV light area to the whole visible light area.
4) We have fabricated and investigated a highly sensitive and stable humidity nanosensor based on alkali metal salts-doped TiO2 nanofibers through electrospinning and calcination techniques. The sensor exhibited excellent characteristics including ultrafast response and recovery behavior, good reproducibility, linearity, and stability. All these characteristics above are very important in humidity detection and control. Moreover, our method provided a useful platform to design and construct highly effective humidity nanodetectors.
引文
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