【摘要】：MOFs器件化已經(jīng)成為MOFs領(lǐng)域的研究熱門,由于高分子鏈柔順、易于加工,因此MOFs與高分子的功能復(fù)合材料的研究受到了廣泛的關(guān)注。其中MOFs膜材料具有高效、節(jié)能、經(jīng)濟等特點,且應(yīng)用范圍可以拓展到液態(tài)及某些氣態(tài)介質(zhì),如膜分離、熒光傳感等領(lǐng)域,因而尤其重視其發(fā)展。本文制備了Ui O-66-NH2晶體與聚氨酯、后修飾雙鍵的Ui O-66-NH2與聚硅氧烷通過化學(xué)鍵交聯(lián)制備得到的金屬有機框架-聚合物膜材料,并且研究了金屬有機框架-聚氨酯膜材料在廢水中染料吸附及分離的性能,金屬有機框架-聚硅氧烷交聯(lián)膜作為膜反應(yīng)器在催化方面的性能。除此之外,本文將MOFs后修飾上具有p H響應(yīng)性的聚合物鏈,并將此MOF用于Pickering乳液的顆粒乳化劑,應(yīng)用于界面反應(yīng)的催化及分離。I.利用Ui O-66-NH2晶體中氨基與聚氨酯預(yù)聚體中異氰酸酯基的反應(yīng),化學(xué)交聯(lián)成膜,且此金屬有機框架-聚氨酯交聯(lián)膜對孔雀石綠、亞甲基藍、羅丹明B以及曙紅Y具有不同的吸附效果。因此,將其作為過濾膜有效分離了曙紅Y與亞甲基藍的混合溶液,以及羅丹明B與孔雀石綠、羅丹明B與亞甲基藍的混合溶液。II.利用表面修飾雙鍵的Ui O-66-NH2晶體,通過巰基-雙鍵Click反應(yīng)與含巰基的聚硅氧烷反應(yīng),得到金屬有機框架-聚硅氧烷化學(xué)交聯(lián)膜。在此基礎(chǔ)上,金屬有機框架-聚硅氧烷化學(xué)交聯(lián)膜負載上金納米顆粒,使得其富有貴金屬的催化能力。將此化學(xué)交聯(lián)膜及金-金屬有機框架-聚硅氧烷化學(xué)交聯(lián)膜應(yīng)用為膜反應(yīng)器,其中不負載金的膜可以利用MOFs的自身的催化性能催化4-硝基苯甲醛與丙二腈的Knoevenagel縮合反應(yīng),而負載金納米顆粒的膜材料能夠協(xié)同貴金屬的催化作用催化4-硝基苯酚還原為4-氨基苯酚。III.在表面修飾雙鍵的MOF上后修飾上具有p H響應(yīng)性官能團的聚合物鏈,利用核磁、紅外、粉末衍射、熱重、透射電鏡、掃描電鏡等測試表征了其結(jié)構(gòu)。將此MOF作為皮克林(Pickering)乳液顆粒乳化劑,制備了Pickering乳液,并研究了其界面催化及分離的性能。研究表明,本文設(shè)計合成的金屬有機框架-高分子化學(xué)交聯(lián)膜、基于金屬有機框架的Pickering乳液,均很好的將高分子與金屬有機框架聯(lián)結(jié)起來,使得金屬有機框架器件化,并且研究表明這兩種膜在染料分離、有機催化方面具有良好的性能,以上研究工作,將金屬有機框架與高分子二者的功能結(jié)合起來,為金屬有機框架器件化提供了一種有效的方法,拓寬了金屬有機框架的應(yīng)用范圍。
[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.
【學(xué)位授予單位】：山東師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TB332
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本文編號：2457108