金属有机框架—高分子功能复合材料的构建及性能研究
发布时间：2019-04-12 14:39
【摘要】：MOFs器件化已经成为MOFs领域的研究热门,由于高分子链柔顺、易于加工,因此MOFs与高分子的功能复合材料的研究受到了广泛的关注。其中MOFs膜材料具有高效、节能、经济等特点,且应用范围可以拓展到液态及某些气态介质,如膜分离、荧光传感等领域,因而尤其重视其发展。本文制备了Ui O-66-NH2晶体与聚氨酯、后修饰双键的Ui O-66-NH2与聚硅氧烷通过化学键交联制备得到的金属有机框架-聚合物膜材料,并且研究了金属有机框架-聚氨酯膜材料在废水中染料吸附及分离的性能,金属有机框架-聚硅氧烷交联膜作为膜反应器在催化方面的性能。除此之外,本文将MOFs后修饰上具有p H响应性的聚合物链,并将此MOF用于Pickering乳液的颗粒乳化剂,应用于界面反应的催化及分离。I.利用Ui O-66-NH2晶体中氨基与聚氨酯预聚体中异氰酸酯基的反应,化学交联成膜,且此金属有机框架-聚氨酯交联膜对孔雀石绿、亚甲基蓝、罗丹明B以及曙红Y具有不同的吸附效果。因此,将其作为过滤膜有效分离了曙红Y与亚甲基蓝的混合溶液,以及罗丹明B与孔雀石绿、罗丹明B与亚甲基蓝的混合溶液。II.利用表面修饰双键的Ui O-66-NH2晶体,通过巯基-双键Click反应与含巯基的聚硅氧烷反应,得到金属有机框架-聚硅氧烷化学交联膜。在此基础上,金属有机框架-聚硅氧烷化学交联膜负载上金纳米颗粒,使得其富有贵金属的催化能力。将此化学交联膜及金-金属有机框架-聚硅氧烷化学交联膜应用为膜反应器,其中不负载金的膜可以利用MOFs的自身的催化性能催化4-硝基苯甲醛与丙二腈的Knoevenagel缩合反应,而负载金纳米颗粒的膜材料能够协同贵金属的催化作用催化4-硝基苯酚还原为4-氨基苯酚。III.在表面修饰双键的MOF上后修饰上具有p H响应性官能团的聚合物链,利用核磁、红外、粉末衍射、热重、透射电镜、扫描电镜等测试表征了其结构。将此MOF作为皮克林(Pickering)乳液颗粒乳化剂,制备了Pickering乳液,并研究了其界面催化及分离的性能。研究表明,本文设计合成的金属有机框架-高分子化学交联膜、基于金属有机框架的Pickering乳液,均很好的将高分子与金属有机框架联结起来,使得金属有机框架器件化,并且研究表明这两种膜在染料分离、有机催化方面具有良好的性能,以上研究工作,将金属有机框架与高分子二者的功能结合起来,为金属有机框架器件化提供了一种有效的方法,拓宽了金属有机框架的应用范围。
[Abstract]:Component-based MOFs has become a hot research field in the field of MOFs. Because of the flexibility and easy processing of polymer chains, the research on functional composites of MOFs and polymer has been paid more and more attention. Among them, MOFs membrane materials have the characteristics of high efficiency, energy saving and economy, and can be extended to liquid and some gaseous media, such as membrane separation, fluorescence sensing and so on. Therefore, the development of MOFs membrane materials is especially important. In this paper, we prepared Ui O-66-NH2 crystal and polyurethane, then modified double bond Ui O-66-NH2 and polysiloxane through chemical bond cross-linking to prepare organometallic framework-polymer membrane material. The adsorption and separation performance of organometallic frame-polyurethane membrane material in wastewater and the catalytic performance of organometallic frame-polysiloxane crosslinked membrane as membrane reactor were also studied. In addition, the polymerization chain with p-H response was modified by MOFs, and the MOF was used as the particle emulsifier of Pickering emulsion to catalyze and separate the interfacial reaction. By means of the reaction of amino group in Ui O-66-NH2 crystal with isocyanate group in polyurethane prepolymer, the film was chemically crosslinked, and the metal organic framework-polyurethane crosslinked film was used for malachite green, methylene blue, and so on. Rhodamine B and eosin Y have different adsorption effects. Therefore, the mixed solution of eosin Y and methylene blue and the mixed solution of rhodamine B and malachite green, rhodamine B and methylene blue were effectively separated as filter membranes. The organometallic framework-polysiloxane chemical crosslinked film was prepared by the reaction of mercapto-double bond Click reaction with polysiloxane containing sulfhydryl groups in the surface modified double bond Ui O-66-NH2 crystal. On the basis of this, gold nanoparticles are loaded on the organometallic framework-polysiloxane chemical crosslinked membrane, which makes it rich in the catalytic ability of precious metals. This chemical crosslinked membrane and gold-organometallic framework-polysiloxane chemical crosslinked membrane were used as membrane reactor, in which the gold-free membrane could catalyze the Knoevenagel condensation reaction of 4-nitrobenzaldehyde with malononitrile by using the catalytic performance of MOFs, and the gold-free membrane could be used to catalyze the Knoevenagel condensation of 4-nitrobenzaldehyde with malononitrile. However, gold nanoparticles supported membrane materials can cooperate with noble metals to catalyze the reduction of 4-nitrophenol to 4-aminophenol. The structure of MOF was characterized by NMR, IR, powder diffraction, thermogravimetry, transmission electron microscopy and scanning electron microscopy. The MOF emulsion was used as the particle emulsifier of Pickering (Pickering) emulsion to prepare the Pickering emulsion. The interfacial catalysis and separation performance of the Pickering emulsion were studied. The results show that the organometallic frame-polymer chemical crosslinked membrane designed and synthesized in this paper, and the Pickering emulsion based on metal-organic framework, are all well connected with the organometallic frame, which makes the organometallic frame part-oriented. The results show that the two membranes have good performance in dyestuff separation and organic catalysis. The above research work combines the functions of organometallic framework and macromolecule, and the results show that these two membranes have good performance in the separation of dyes and organic catalysis. This paper provides an effective method for metal-organic frame component, and widens the application range of metal-organic frame.
【学位授予单位】：山东师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB332
，
本文编号：2457108
[Abstract]:Component-based MOFs has become a hot research field in the field of MOFs. Because of the flexibility and easy processing of polymer chains, the research on functional composites of MOFs and polymer has been paid more and more attention. Among them, MOFs membrane materials have the characteristics of high efficiency, energy saving and economy, and can be extended to liquid and some gaseous media, such as membrane separation, fluorescence sensing and so on. Therefore, the development of MOFs membrane materials is especially important. In this paper, we prepared Ui O-66-NH2 crystal and polyurethane, then modified double bond Ui O-66-NH2 and polysiloxane through chemical bond cross-linking to prepare organometallic framework-polymer membrane material. The adsorption and separation performance of organometallic frame-polyurethane membrane material in wastewater and the catalytic performance of organometallic frame-polysiloxane crosslinked membrane as membrane reactor were also studied. In addition, the polymerization chain with p-H response was modified by MOFs, and the MOF was used as the particle emulsifier of Pickering emulsion to catalyze and separate the interfacial reaction. By means of the reaction of amino group in Ui O-66-NH2 crystal with isocyanate group in polyurethane prepolymer, the film was chemically crosslinked, and the metal organic framework-polyurethane crosslinked film was used for malachite green, methylene blue, and so on. Rhodamine B and eosin Y have different adsorption effects. Therefore, the mixed solution of eosin Y and methylene blue and the mixed solution of rhodamine B and malachite green, rhodamine B and methylene blue were effectively separated as filter membranes. The organometallic framework-polysiloxane chemical crosslinked film was prepared by the reaction of mercapto-double bond Click reaction with polysiloxane containing sulfhydryl groups in the surface modified double bond Ui O-66-NH2 crystal. On the basis of this, gold nanoparticles are loaded on the organometallic framework-polysiloxane chemical crosslinked membrane, which makes it rich in the catalytic ability of precious metals. This chemical crosslinked membrane and gold-organometallic framework-polysiloxane chemical crosslinked membrane were used as membrane reactor, in which the gold-free membrane could catalyze the Knoevenagel condensation reaction of 4-nitrobenzaldehyde with malononitrile by using the catalytic performance of MOFs, and the gold-free membrane could be used to catalyze the Knoevenagel condensation of 4-nitrobenzaldehyde with malononitrile. However, gold nanoparticles supported membrane materials can cooperate with noble metals to catalyze the reduction of 4-nitrophenol to 4-aminophenol. The structure of MOF was characterized by NMR, IR, powder diffraction, thermogravimetry, transmission electron microscopy and scanning electron microscopy. The MOF emulsion was used as the particle emulsifier of Pickering (Pickering) emulsion to prepare the Pickering emulsion. The interfacial catalysis and separation performance of the Pickering emulsion were studied. The results show that the organometallic frame-polymer chemical crosslinked membrane designed and synthesized in this paper, and the Pickering emulsion based on metal-organic framework, are all well connected with the organometallic frame, which makes the organometallic frame part-oriented. The results show that the two membranes have good performance in dyestuff separation and organic catalysis. The above research work combines the functions of organometallic framework and macromolecule, and the results show that these two membranes have good performance in the separation of dyes and organic catalysis. This paper provides an effective method for metal-organic frame component, and widens the application range of metal-organic frame.
【学位授予单位】：山东师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB332
，
本文编号：2457108
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