模板法宏量制備納米酚醛樹脂基復合材料及功能化研究
發(fā)布時間：2018-08-09 07:53
【摘要】：聚合物納米結構材料擁有獨特的物理及化學性質(zhì),在人們的日常生活中發(fā)揮著非常重要的作用。酚醛樹脂(PFR),作為一種傳統(tǒng)的高分子材料,近年來隨著納米技術的快速發(fā)展,探索新的方法制備新的納米酚醛樹脂基復合材料也成為一個新的研究熱點。為改善此類材料的性能和拓展其實際應用,我們發(fā)展了模板誘導宏量合成的方法分別制備出系列一維苯酚甲醛樹脂基納米材料和三維間苯二酚-甲醛樹脂(RF)／氧化石墨烯(GO)復合氣凝膠材料�；谏鲜霾牧�,我們分別對其進行了功能化探索研究,研究了此類新材料在環(huán)境,生物,能源等方面的應用。取得的主要研究結果總結如下： 1.建立了一維納米模板誘導水熱聚合宏量制備系列一維酚醛樹脂基納米材料的新方法。通過采用不同的一維納米材料為模板[超細碲(Te)納米線、短的碲納米棒和銀納米線)],合成出多種以PFR為殼層的納米電纜結構。其中,對于Te@PFR納米電纜,我們詳細研究了反應物濃度、時間以及溫度對最終產(chǎn)物形貌的影響,從而經(jīng)過分析提出了它們的合成機理。此外,利用氫氧化鈉水溶液去除中心的碲核后,可以得到純的PFR納米纖維。這些研究都為這種一維酚醛樹脂基納米材料的后續(xù)應用奠定了良好的基礎。 2.探索了一維酚醛樹脂基納米材料的在污水處理、光熱治療、構筑超疏水自清潔涂層等方面的多功能應用研究。純的PFR納米纖維由于表面含有豐富的含氧基團(OH)、苯環(huán)和含氮基團等官能團,因此它們對剛果紅染料和重金屬六價鉻離子具有很優(yōu)異的吸附性能。同時利用抽濾的方法,可以制得相應的PFR納米纖維膜,經(jīng)過研究,我們發(fā)現(xiàn)它們在流動相溶液中也可以很高效的去除剛果紅染料。通過實驗證明了我們合成出的這種新型的PFR納米纖維在水污染處理方面具有潛在的應用前景；另一方面,我們通過氯金酸根與碲納米線的模板置換反應,制備出了一種具有出色光熱治療效果的豌豆莢狀Au@PFR納米纖維；此外,基于合成出的PFR納米項鏈的特殊形貌,同時利用它們在水溶液中良好的分散性,我們發(fā)展了一種噴涂的技術在不同基底上構筑超疏水表面。 3.建立了模板誘導聚合法宏量制備一系列新型間苯二酚甲醛樹脂-氧化石墨烯(RF-GO)復合氣凝膠的新技術。在合成過程中,氧化石墨烯片起著模板骨架的作用,金屬離子(Co2+,Ni2+,或Ca2+)則是作為催化劑和連接劑。通過改變反應條件,我們可以對這種氣凝膠的表觀密度和力學性能進行調(diào)節(jié)。特別地,在合適的反應條件下,我們可以制備出一種高度可壓縮的RF-GO-金屬氣凝膠,相比于傳統(tǒng)的脆性RF氣凝膠,這種新型的復合氣凝膠能夠耐受高達80%的壓縮形變,并且釋放壓力之后就可以快速恢復至初始形貌。它們這種優(yōu)異的力學性能歸功于反應中引入的氧化石墨烯和金屬離子的協(xié)同效應。利用這種氣凝膠超高的可壓縮性能,我們探索了它們作為一種固體吸附劑在污水處理方面的應用。 4.基于上述合成的RF-GO-Co復合氣凝膠,通過高溫裂解的方法制備出一種新穎的具有超低密度(9mg/cm3)和超順磁性的鈷摻雜碳氣凝膠,并且發(fā)現(xiàn)它們在溢油處理和電催化方面具有優(yōu)異的性能。這種碳氣凝膠主要由厚度為50nm的相互連接的片層結構組成。超低密度和疏水性質(zhì)導致這種碳氣凝膠可以作為各種油類和有機溶劑的高效吸附劑(最高吸附容量為自身重量的132倍)。此外,由于在這種碳氣凝膠內(nèi)部存在含鈷納米顆粒,因此它們在氧氣還原反應方面也表現(xiàn)出優(yōu)異的電催化活性和穩(wěn)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.
【學位授予單位】：中國科學技術大學
【學位級別】：博士
【學位授予年份】：2015
【分類號】：TB383.1;TB33
本文編號：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.
【學位授予單位】：中國科學技術大學
【學位級別】：博士
【學位授予年份】：2015
【分類號】：TB383.1;TB33
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