本文關(guān)鍵詞： 金屬有機(jī)骨架 沸石咪唑酯類膜 可規(guī)模放大合成 嵌入改性 氣體分離　出處：《浙江工業(yè)大學(xué)》2015年碩士論文　論文類型：學(xué)位論文

【摘要】：金屬有機(jī)骨架(MOF_s)是一種新型的多孔晶體材料,具有規(guī)則的孔道結(jié)構(gòu)以及豐富的物理、化學(xué)性質(zhì),并且可以通過合理地設(shè)計(jì)對其進(jìn)行結(jié)構(gòu)上和性質(zhì)上的改變,因此,MOF_s材料在吸附、分離、催化、傳感等領(lǐng)域展現(xiàn)出了廣闊的應(yīng)用前景。在近十年間,通過自組裝而形成的MOF膜在分離領(lǐng)域取得了驚人的發(fā)展。目前,越來越多的研究團(tuán)隊(duì)在MOF膜材料、合成方法和分離性能等方面均取得了矚目的成績。然而,從工業(yè)應(yīng)用的角度來考慮,MOF膜在合成方法和分離性能方面仍然很難滿足實(shí)際需求,發(fā)展進(jìn)入到了瓶頸時(shí)期。基于上述考慮,本文以ZIF-8為目標(biāo)MOF材料,分別從合成方法和分離性能兩個(gè)方面進(jìn)行了研究。首先,本工作從合成方法的角度出發(fā),結(jié)合膜接觸器和界面合成的理論提出了一種新型可規(guī)模放大的MOF膜合成方法,這種方法擺脫了傳統(tǒng)的高能耗的溶劑熱的過程,避免MOF膜在裝填過程中被破壞的風(fēng)險(xiǎn),利用了界面合成的原理可以避免均相成核而導(dǎo)致的原料的浪費(fèi)。利用這種方法,我們成功合成了連續(xù)的ZIF-8膜。我們采用SEM、XRD、EDS等手段對合成的ZIF-8膜進(jìn)行了表征,確定了ZIF-8膜的形貌、結(jié)構(gòu)方面的特征。通過考察前驅(qū)溶液濃度比例和合成時(shí)間對成膜的影響,我們初步分析了MOF膜的成膜機(jī)理,為后續(xù)其它種類的MOF膜的合成提供了理論支持。另一方面,為了提高M(jìn)OF膜的分離性能,本工作在新型合成方法的基礎(chǔ)上成功合成了聚合物(聚乙烯吡咯烷酮,PVP)嵌入的ZIF-8膜。聚合物在MOF中的嵌入使得MOF孔道結(jié)構(gòu)發(fā)生改變,同時(shí)還能促進(jìn)MOF晶體之間的互生生長,有效地減少甚至消除MOF膜中的納米級缺陷,從而大幅提高M(jìn)OF膜的氣體分離性能。實(shí)驗(yàn)結(jié)果顯示,PVP嵌入后ZIF-8顆粒變小,ZIF-8膜結(jié)構(gòu)更加致密。通過對PVP嵌入的ZIF-8顆粒進(jìn)行XRD、N2吸附測試和對ZIF-8復(fù)合膜進(jìn)行FTIR表征,證明了PVP在ZIF-8中可嵌入性。最后我們對合成的PVP嵌入ZIF-8膜進(jìn)行單組分氣體滲透測試,實(shí)驗(yàn)結(jié)果顯示相比于純的ZIF-8膜,PVP嵌入ZIF-8膜氣體通量有一定的降低,但H_2/CO_2理想分離選擇性從4.97提高到了52.71,該值遠(yuǎn)遠(yuǎn)超過了大多數(shù)MOF膜對H_2/CO_2體系的分離效果。
[Abstract]:Organometallic organic frameworks (MOFs) is a new porous crystal material with regular pore structure and abundant physical and chemical properties. And the structure and properties of MOFs can be changed by reasonable design. Therefore, MOFs materials in adsorption, separation, catalysis, sensing and other fields have shown a broad application prospects in the recent decade. MOF membranes formed by self-assembly have made remarkable progress in the field of separation. At present, more and more research teams are in the field of MOF membrane materials. Remarkable achievements have been made in synthesis methods and separation properties. However, it is still difficult to meet the practical requirements of synthesis and separation properties of MOF membranes from the point of view of industrial application. The development has entered the bottleneck period. Based on the above considerations, the synthesis method and separation performance of ZIF-8 as the target MOF materials are studied in this paper. First of all. In this paper, from the point of view of synthesis method, a novel scalable MOF membrane synthesis method is proposed, which combines the theory of membrane contactor and interface synthesis. This method avoids the traditional solvothermal process of high energy consumption and avoids the risk of MOF film being destroyed in the filling process. The waste of raw materials caused by homogeneous nucleation can be avoided by using the principle of interfacial synthesis. Using this method, we have successfully synthesized continuous ZIF-8 films. The synthesized ZIF-8 films were characterized by EDS, and the morphology and structure of ZIF-8 films were determined. The effects of concentration ratio of precursor solution and synthesis time on the formation of ZIF-8 films were investigated. We preliminarily analyzed the mechanism of MOF membrane formation, which provided theoretical support for the subsequent synthesis of other kinds of MOF membrane. On the other hand, in order to improve the separation performance of MOF membrane. Based on the new synthesis method, the ZIF-8 film embedded in polyvinylpyrrolidone (PVP) was successfully synthesized. The intercalation of the polymer in MOF changed the pore structure of MOF. At the same time, it can promote the mutual growth of MOF crystals, reduce or even eliminate the nano-scale defects in MOF films, thus greatly improve the gas separation performance of MOF films. The experimental results show that. The structure of ZIF-8 membrane became denser after ZIF-8 particles were embedded in PVP. XRD was carried out on ZIF-8 particles embedded in PVP. N2 adsorption test and FTIR characterization of ZIF-8 composite membrane. The embeddedness of PVP in ZIF-8 was proved. Finally, we tested the PVP embedded ZIF-8 membrane by one component gas permeation test, and the experimental results showed that compared with the pure ZIF-8 membrane. The gas flux of PVP embedded in ZIF-8 membrane decreased to a certain extent, but the ideal separation selectivity of H _ 2 / COS _ 2 increased from 4.97 to 52.71. This value far exceeds the separation effect of most MOF membranes on the HSP 2 / COSP 2 system.
【學(xué)位授予單位】：浙江工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：TQ051.893

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