本文選題：多孔有機聚合物 + 配位聚合物��； 參考：《山東理工大學(xué)》2017年碩士論文

【摘要】：多孔有機骨架材料(Porous Organic Frameworks,POFs)由于其較大的比表面積和可調(diào)節(jié)功能化,合成方法多樣等優(yōu)點受到廣大科學(xué)研究者廣泛關(guān)注。在近二十年間,具有多孔性質(zhì)的結(jié)晶態(tài)的多孔配位聚合物(Porous Coordination Polymer,PCPs),以及一種通過共價鍵連接而形成的多孔有機聚合物材料(Porous Organic Polymers,POPs)成為了科學(xué)家們的研究熱點,也為多孔材料的研究開辟了另一個嶄新的領(lǐng)域。目前,配位聚合物材料和多孔有機聚合物材料已經(jīng)被廣泛的應(yīng)用于催化、離子傳感、氣體存儲、氣體分離、光催化、電池及超級電容器、離子交換、質(zhì)子傳導(dǎo)以及藥物傳輸釋放等領(lǐng)域。本論文中首先合成了多孔有機聚合物的模型化合物P,在模型化合物的基礎(chǔ)上成功合成了新型的多孔有機聚合物。其次,采用帶有修飾基團(tuán)的有機配體作為次級構(gòu)筑單元,通過溶劑熱法合成了新型的熒光配位聚合物材料。首先,合成了1,3,5-三醛基均苯三酚,將其與萘酰亞胺衍生物通過希夫堿反應(yīng)合成出了多孔有機聚合物的模型化合物P,并采用核磁共振氫譜和元素分析對其結(jié)構(gòu)進(jìn)行表征,并且研究了模型化合物P作為熒光離子探針的性質(zhì)。結(jié)果表明,在DMSO溶液中,化合物P對Fe~(2+)和Cu~(2+)同時表現(xiàn)出熒光淬滅現(xiàn)象,并且P的熒光淬滅程度與溶液中Fe~(2+)離子濃度呈線性關(guān)系;另外,化合物P與Fe~(2+)離子形成金屬復(fù)合物P-Fe,該復(fù)合物的熒光能夠高選擇性的被陰離子H_2PO_4~-增強,溶液的熒光強度隨著H_2PO_4~-濃度的增加而線性增加,即P-Fe可以通過“關(guān)-開”模式選擇性的熒光傳感H_2PO_4~-離子,金屬復(fù)合物P-Fe對H_2PO_4~-的檢出限為1.897×10-7mol/L。其次,基于模型化合物P的結(jié)構(gòu)和性質(zhì),我們通過調(diào)整萘酰亞胺衍生物的結(jié)構(gòu),成功得到了多孔有機聚合物,命名為POP-1(Porous Organic Polymers 1),我們采用粉末X射線衍射,氮氣吸附,熱重分析對其進(jìn)行了表征,并且研究了POP-1作為催化劑光降解染料羅丹明B的性質(zhì)。研究發(fā)現(xiàn),POP-1對羅丹明B具有較高的催化活性,在經(jīng)過三次重復(fù)的催化反應(yīng)后,其活性基本沒有下降,并且自然光條件下仍然可以高效的催化降解RhB。另外,對POP-1的光催化實驗過程進(jìn)行了動力學(xué)研究,實驗結(jié)果表明溫度的升高有利于光催化反應(yīng)的進(jìn)行,降解反應(yīng)的活化能為82.37 kJ/mol。最后,利用含有氨基活性基團(tuán)的2-氨基對苯二甲酸與2,2?-聯(lián)吡啶作為有機配體,與金屬鎘制備出一種多孔的配位聚合物1。X射線粉末衍射(XRD)、元素分析以及熱重分析(TGA)對其進(jìn)行表征,并對其性質(zhì)進(jìn)行研究。實驗發(fā)現(xiàn),配位聚合物1具有作為熒光探針檢測Cu~(2+)以及小分子環(huán)己烷的性質(zhì)。
[Abstract]:Porous Organic frameworks (POFs) has attracted wide attention due to its large specific surface area, adjustable functionalization and various synthesis methods. In the last two decades, porous Coordination polymeric PCPs, a crystalline porous coordination polymer, and a kind of porous organic polymer material, Porous Organic PolymersPOPss, have become the focus of scientists. It also opens up another new field for the study of porous materials. At present, coordination polymer materials and porous organic polymer materials have been widely used in catalysis, ion sensing, gas storage, gas separation, photocatalysis, batteries and supercapacitors, ion exchange, Proton conduction and drug transport and release and other fields. In this paper, we first synthesized the porous organic polymer model compound, and based on the model compound, we successfully synthesized a new porous organic polymer. Secondly, novel fluorescent coordination polymer materials were synthesized by solvothermal method using organic ligands with modified groups as secondary building units. Firstly, the model compound P of porous organic polymer was synthesized by Schiff base reaction, and the structure of the model compound was characterized by nuclear magnetic resonance (NMR) and elemental analysis. The properties of the model compound P as a fluorescent ion probe were also studied. The results show that in DMSO solution, compound P exhibits fluorescence quenching phenomenon for both Fe~(2) and Cu~(2, and the fluorescence quenching degree of P is linearly related to the concentration of Fe~(2) ions in the solution, in addition, there is a linear relationship between the fluorescence quenching degree of P and the concentration of Fe~(2 ion in the solution. Compound P and Fe~(2) ions form a metal complex P-Fe.The fluorescence of the complex can be enhanced by highly selective anionic H2PO4-, and the fluorescence intensity of the solution increases linearly with the increase of H2PO4- concentration. That is to say, P-Fe can detect H2PO4- ion through "turn-on" mode selective fluorescence sensing, and metal complex P-Fe has a detection limit of 1.897 脳 10 ~ (-7) mol 路L ~ (-1) for H _ 2PO _ (4). Secondly, based on the structure and properties of model compound P, we successfully obtained the porous organic polymer, named POP-1(Porous Organic Polymers 1, by adjusting the structure of naphthalimide derivatives. We used powder X-ray diffraction and nitrogen adsorption. It was characterized by thermogravimetric analysis and the photodegradation of Rhodamine B by POP-1 as catalyst was studied. It was found that POP-1 had high catalytic activity for Rhodamine B, and after three repeated catalytic reactions, the activity of POP-1 did not decrease and RhB could be degraded efficiently under natural light condition. In addition, the kinetics of photocatalytic reaction of POP-1 was studied. The experimental results showed that the increase of temperature was beneficial to the photocatalytic reaction, and the activation energy of the degradation reaction was 82.37 kJ / mol. Finally, a porous coordination polymer, XRDX, characterized by elemental analysis and thermogravimetric analysis (TGA), was prepared by using 2-aminoterephthalic acid and 2Aminoterephthalic acid as organic ligands and cadmium as organic ligands, respectively, by X-ray powder diffraction (XRD), elemental analysis and thermogravimetric analysis (TGA). And its properties are studied. It is found that the coordination polymer 1 has the properties of detecting Cu~(2 as a fluorescent probe and cyclohexane as a small molecule.
【學(xué)位授予單位】：山東理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O641.4;TB383.4

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本文編號：1796683