模板法宏量制备纳米酚醛树脂基复合材料及功能化研究
发布时间：2018-08-09 07:53
【摘要】：聚合物纳米结构材料拥有独特的物理及化学性质,在人们的日常生活中发挥着非常重要的作用。酚醛树脂(PFR),作为一种传统的高分子材料,近年来随着纳米技术的快速发展,探索新的方法制备新的纳米酚醛树脂基复合材料也成为一个新的研究热点。为改善此类材料的性能和拓展其实际应用,我们发展了模板诱导宏量合成的方法分别制备出系列一维苯酚甲醛树脂基纳米材料和三维间苯二酚-甲醛树脂(RF)／氧化石墨烯(GO)复合气凝胶材料。基于上述材料,我们分别对其进行了功能化探索研究,研究了此类新材料在环境,生物,能源等方面的应用。取得的主要研究结果总结如下： 1.建立了一维纳米模板诱导水热聚合宏量制备系列一维酚醛树脂基纳米材料的新方法。通过采用不同的一维纳米材料为模板[超细碲(Te)纳米线、短的碲纳米棒和银纳米线)],合成出多种以PFR为壳层的纳米电缆结构。其中,对于Te@PFR纳米电缆,我们详细研究了反应物浓度、时间以及温度对最终产物形貌的影响,从而经过分析提出了它们的合成机理。此外,利用氢氧化钠水溶液去除中心的碲核后,可以得到纯的PFR纳米纤维。这些研究都为这种一维酚醛树脂基纳米材料的后续应用奠定了良好的基础。 2.探索了一维酚醛树脂基纳米材料的在污水处理、光热治疗、构筑超疏水自清洁涂层等方面的多功能应用研究。纯的PFR纳米纤维由于表面含有丰富的含氧基团(OH)、苯环和含氮基团等官能团,因此它们对刚果红染料和重金属六价铬离子具有很优异的吸附性能。同时利用抽滤的方法,可以制得相应的PFR纳米纤维膜,经过研究,我们发现它们在流动相溶液中也可以很高效的去除刚果红染料。通过实验证明了我们合成出的这种新型的PFR纳米纤维在水污染处理方面具有潜在的应用前景；另一方面,我们通过氯金酸根与碲纳米线的模板置换反应,制备出了一种具有出色光热治疗效果的豌豆荚状Au@PFR纳米纤维；此外,基于合成出的PFR纳米项链的特殊形貌,同时利用它们在水溶液中良好的分散性,我们发展了一种喷涂的技术在不同基底上构筑超疏水表面。 3.建立了模板诱导聚合法宏量制备一系列新型间苯二酚甲醛树脂-氧化石墨烯(RF-GO)复合气凝胶的新技术。在合成过程中,氧化石墨烯片起着模板骨架的作用,金属离子(Co2+,Ni2+,或Ca2+)则是作为催化剂和连接剂。通过改变反应条件,我们可以对这种气凝胶的表观密度和力学性能进行调节。特别地,在合适的反应条件下,我们可以制备出一种高度可压缩的RF-GO-金属气凝胶,相比于传统的脆性RF气凝胶,这种新型的复合气凝胶能够耐受高达80%的压缩形变,并且释放压力之后就可以快速恢复至初始形貌。它们这种优异的力学性能归功于反应中引入的氧化石墨烯和金属离子的协同效应。利用这种气凝胶超高的可压缩性能,我们探索了它们作为一种固体吸附剂在污水处理方面的应用。 4.基于上述合成的RF-GO-Co复合气凝胶,通过高温裂解的方法制备出一种新颖的具有超低密度(9mg/cm3)和超顺磁性的钴掺杂碳气凝胶,并且发现它们在溢油处理和电催化方面具有优异的性能。这种碳气凝胶主要由厚度为50nm的相互连接的片层结构组成。超低密度和疏水性质导致这种碳气凝胶可以作为各种油类和有机溶剂的高效吸附剂(最高吸附容量为自身重量的132倍)。此外,由于在这种碳气凝胶内部存在含钴纳米颗粒,因此它们在氧气还原反应方面也表现出优异的电催化活性和稳定性。
[Abstract]:Polymer nanomaterials have unique physical and chemical properties and play a very important role in people's daily life. As a traditional polymeric material, phenolic resin (PFR), with the rapid development of nanotechnology in recent years, has become a new method to prepare new nano phenolic resin matrix composites. In order to improve the performance of this kind of material and expand its practical application, we have developed a series of one-dimensional phenol formaldehyde resin based nanomaterials and three dimensional resorcinol formaldehyde resin (RF) / graphene oxide (GO) compound aerogels respectively. The main results are summarized as follows:1.
1. a new method for the preparation of a series of one-dimensional phenolic resin based nanomaterials with one-dimensional nano template induced hydrothermal polymerization was established. By using different one-dimensional nanomaterials as templates [ultrafine tellurium (Te) nanowires, short tellurium nanorods and silver nanowires], a variety of nano cable structures with PFR shell were synthesized. Among them, the Te@PFR nanowires were used. We studied the influence of the concentration, time and temperature of the reactants on the morphology of the final product in detail, and then the synthesis mechanism of the final product was analyzed. In addition, the pure PFR nanofibers can be obtained after the removal of the core tellurium from the sodium hydroxide solution. These studies have been followed by the follow-up of the one dimensional phenolic resin based nanomaterials. The application laid a good foundation.
2. the multifunctional application of one dimensional phenolic resin based nanomaterials in sewage treatment, photothermal treatment, and superhydrophobic self cleaning coating was studied. Pure PFR nanofibers have functional groups such as rich oxygen group (OH), benzene ring and nitrogen containing groups on the surface, because of these, they have six valence chromium ion with Congo red dye and heavy metal. It has excellent adsorption properties. At the same time, the corresponding PFR nanofibric membrane can be obtained by the method of pumping. After study, we find that they can also effectively remove the Congo red dye in the liquid phase solution. It has been proved by experiments that the new PFR nanofibers we synthesized have potential in water pollution treatment. On the other hand, we have prepared a pea pod like Au@PFR nanofiber with excellent photothermal treatment through the template replacement reaction of chlorauric acid and tellurium nanowires. In addition, based on the special morphology of the synthesized PFR nanoscale necklace, and using their good dispersibility in the aqueous solution, we developed a new type of nanofibrils. Spray technology is used to construct super hydrophobic surfaces on different substrates.
3. a new technology for the preparation of a series of new resorcinol formaldehyde resin - RF-GO composite aerogels was established by template induction polymerization. In the process of synthesis, the graphene oxide tablet plays the role of template skeleton, metal ions (Co2+, Ni2+, or Ca2+) are used as catalysts and connecting agents. By changing the reaction conditions, we can In order to regulate the apparent density and mechanical properties of this aerogel, in particular, we can produce a highly compressible RF-GO- metal aerogel under the appropriate reaction conditions. Compared to the traditional brittle RF aerogels, the new type of composite aerogel can tolerate up to 80% of the compression deformation and release the pressure after the release of the aerogel. Their excellent mechanical properties are attributed to the synergistic effects of graphene oxide and metal ions introduced in the reaction. Using the ultra high compressibility of this aerogel, we explored the application of them as a solid adsorbent in the wastewater treatment.
4. based on the synthesized RF-GO-Co composite aerogels, a novel super low density (9mg/cm3) and superparamagnetic cobalt doped carbon aerogels were prepared by pyrolysis, and they were found to have excellent performance in oil spill treatment and electrocatalysis. This carbon aerogel is mainly composed of interconnected slices with thickness of 50nm. The ultralow density and hydrophobic properties cause this carbon aerogel to be an efficient adsorbent for various oils and organic solvents (the maximum adsorption capacity is 132 times the weight of its own). In addition, because of the presence of cobalt nanoparticles in this kind of carbon aerogel, they also exhibit excellent electricity in the oxygen reduction reaction. Catalytic activity and stability.
【学位授予单位】：中国科学技术大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TB383.1;TB33
本文编号：2173416
[Abstract]:Polymer nanomaterials have unique physical and chemical properties and play a very important role in people's daily life. As a traditional polymeric material, phenolic resin (PFR), with the rapid development of nanotechnology in recent years, has become a new method to prepare new nano phenolic resin matrix composites. In order to improve the performance of this kind of material and expand its practical application, we have developed a series of one-dimensional phenol formaldehyde resin based nanomaterials and three dimensional resorcinol formaldehyde resin (RF) / graphene oxide (GO) compound aerogels respectively. The main results are summarized as follows:1.
1. a new method for the preparation of a series of one-dimensional phenolic resin based nanomaterials with one-dimensional nano template induced hydrothermal polymerization was established. By using different one-dimensional nanomaterials as templates [ultrafine tellurium (Te) nanowires, short tellurium nanorods and silver nanowires], a variety of nano cable structures with PFR shell were synthesized. Among them, the Te@PFR nanowires were used. We studied the influence of the concentration, time and temperature of the reactants on the morphology of the final product in detail, and then the synthesis mechanism of the final product was analyzed. In addition, the pure PFR nanofibers can be obtained after the removal of the core tellurium from the sodium hydroxide solution. These studies have been followed by the follow-up of the one dimensional phenolic resin based nanomaterials. The application laid a good foundation.
2. the multifunctional application of one dimensional phenolic resin based nanomaterials in sewage treatment, photothermal treatment, and superhydrophobic self cleaning coating was studied. Pure PFR nanofibers have functional groups such as rich oxygen group (OH), benzene ring and nitrogen containing groups on the surface, because of these, they have six valence chromium ion with Congo red dye and heavy metal. It has excellent adsorption properties. At the same time, the corresponding PFR nanofibric membrane can be obtained by the method of pumping. After study, we find that they can also effectively remove the Congo red dye in the liquid phase solution. It has been proved by experiments that the new PFR nanofibers we synthesized have potential in water pollution treatment. On the other hand, we have prepared a pea pod like Au@PFR nanofiber with excellent photothermal treatment through the template replacement reaction of chlorauric acid and tellurium nanowires. In addition, based on the special morphology of the synthesized PFR nanoscale necklace, and using their good dispersibility in the aqueous solution, we developed a new type of nanofibrils. Spray technology is used to construct super hydrophobic surfaces on different substrates.
3. a new technology for the preparation of a series of new resorcinol formaldehyde resin - RF-GO composite aerogels was established by template induction polymerization. In the process of synthesis, the graphene oxide tablet plays the role of template skeleton, metal ions (Co2+, Ni2+, or Ca2+) are used as catalysts and connecting agents. By changing the reaction conditions, we can In order to regulate the apparent density and mechanical properties of this aerogel, in particular, we can produce a highly compressible RF-GO- metal aerogel under the appropriate reaction conditions. Compared to the traditional brittle RF aerogels, the new type of composite aerogel can tolerate up to 80% of the compression deformation and release the pressure after the release of the aerogel. Their excellent mechanical properties are attributed to the synergistic effects of graphene oxide and metal ions introduced in the reaction. Using the ultra high compressibility of this aerogel, we explored the application of them as a solid adsorbent in the wastewater treatment.
4. based on the synthesized RF-GO-Co composite aerogels, a novel super low density (9mg/cm3) and superparamagnetic cobalt doped carbon aerogels were prepared by pyrolysis, and they were found to have excellent performance in oil spill treatment and electrocatalysis. This carbon aerogel is mainly composed of interconnected slices with thickness of 50nm. The ultralow density and hydrophobic properties cause this carbon aerogel to be an efficient adsorbent for various oils and organic solvents (the maximum adsorption capacity is 132 times the weight of its own). In addition, because of the presence of cobalt nanoparticles in this kind of carbon aerogel, they also exhibit excellent electricity in the oxygen reduction reaction. Catalytic activity and stability.
【学位授予单位】：中国科学技术大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TB383.1;TB33
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