發(fā)布時間：2018-03-18 05:31

  本文選題：離子熱合成　切入點：質(zhì)子型離子液體　出處：《太原理工大學(xué)》2015年碩士論文　論文類型：學(xué)位論文

【摘要】：磷酸鋁多孔材料作為分子篩的一大類，在催化、吸附及分離等方面具有潛在的應(yīng)用價值，設(shè)計和合成具有新型結(jié)構(gòu)的磷酸鋁材料具有重要的意義。目前，大部分磷酸鋁材料都是在有機胺存在的條件下，通過水熱或溶劑熱途徑合成的，溶劑和有機胺模板劑是影響磷酸鋁骨架結(jié)構(gòu)的重要因素。 離子熱合成法，利用離子液體作為溶劑和模板劑，在新型無機多孔材料的合成方面顯示出獨特的優(yōu)勢。質(zhì)子型離子液體作為離子液體的一個分支，它是通過Br nsted酸和Br nsted堿之間質(zhì)子化轉(zhuǎn)移反應(yīng)形成的，，和傳統(tǒng)的離子液體相比，具有價格便宜、易于提純等優(yōu)勢。論文采用乙酸對有機胺進行質(zhì)子化，得到五種質(zhì)子型離子液體，并用五種質(zhì)子型離子液體作為溶劑和模板劑，研究了新型磷酸鋁材料的合成特點和規(guī)律。通過改變合成條件合成出十種磷酸鋁材料，利用XRD、NMR、TG-DSC、SEM、CHN元素分析等方法對樣品的結(jié)構(gòu)及物化性質(zhì)進行了表征，主要研究內(nèi)容和結(jié)論如下： 1、在質(zhì)子型的3-二甲胺基丙胺離子液體中得到兩種磷酸鋁材料AlPO-PIL1和AlPO-PIL2，HF對相的選擇性起到重要的作用。無HF時，得到的AlPO-PIL1具有一維鏈狀四元環(huán)結(jié)構(gòu)；加入HF后得到AlPO-PIL2二維層狀結(jié)構(gòu)，AlPO-PIL2的模板劑N,N'-二甲基-1,3-丙二胺是在晶化的過程中，質(zhì)子化的3-二甲胺基丙胺發(fā)生分子內(nèi)原位甲基轉(zhuǎn)移得到。 2、在離子熱合成中，以質(zhì)子型的離子液體3-二乙胺基丙胺乙酸鹽作為溶劑和模板劑，得到兩種新型結(jié)構(gòu)的磷酸鋁材料，AlPO-PIL3和AlPO-PIL4。單晶結(jié)構(gòu)解析發(fā)現(xiàn)：在晶化過程中，質(zhì)子化的3-二乙胺基丙胺會發(fā)生乙基化轉(zhuǎn)移生成N,N'-二乙基-1,3-丙二胺，進而得到以N,N'-二乙基-1,3-丙二胺為模板劑的二維層狀結(jié)構(gòu)的AlPO-PIL3。 3、在質(zhì)子型的3-二丁胺基丙胺中得到的兩種具有新型結(jié)構(gòu)的AlPO-PIL5和AlPO-PIL6。CHN元素分析和TG-DSC分析表明：3-二丁氨基丙胺陽離子在晶化的過程中沒有發(fā)生熱分解，最終進入到磷酸鋁骨架中起到平衡骨架電荷的作用。 4、在質(zhì)子型的N,N-四甲基乙二胺和N,N-雙(3-氨丙基)甲胺體系中共合成了四種磷酸鋁材料：AlPO-PIL7、AlPO-PIL8、AlPO-PIL9和AlPO-PIL10。通過單晶結(jié)構(gòu)解析得到了兩種材料的結(jié)構(gòu)，AlPO-PIL7為二維層狀結(jié)構(gòu)，四甲基乙二胺陽離子位于層間平衡骨架電荷。AlPO-PIL9是由四元環(huán)連接而成的一維鏈狀結(jié)構(gòu)。
[Abstract]:As a kind of molecular sieve, aluminum phosphate porous materials have potential application value in catalysis, adsorption and separation. It is of great significance to design and synthesize aluminum phosphate materials with new structure. Most aluminophosphate materials are synthesized by hydrothermal or solvothermal pathways in the presence of organic amines. Solvents and organic amine templates are important factors affecting the skeleton structure of aluminophosphate. Ion-thermal synthesis, using ionic liquids as solvents and templates, has shown unique advantages in the synthesis of new inorganic porous materials, proton ionic liquids as a branch of ionic liquids, Compared with the traditional ionic liquids, it is cheap and easy to purify. In this paper, acetic acid is used to protonize organic amines, which is formed by the proton transfer reaction between Br nsted acid and Br nsted base. Five kinds of proton ionic liquids were obtained, and five kinds of proton ionic liquids were used as solvents and templates to study the synthesis characteristics and rules of new aluminum phosphate materials. Ten kinds of aluminum phosphate materials were synthesized by changing the synthetic conditions. The structure and physicochemical properties of the samples were characterized by means of elemental analysis of XRDNMR-TG-DSC-SEMN. The main contents and conclusions are as follows:. 1. Two kinds of aluminum phosphate materials, AlPO-PIL1 and AlPO-PIL2H, play an important role in the selectivity of phase in proton type 3-dimethylamino propylamine ionic liquid. Without HF, the obtained AlPO-PIL1 has one-dimensional chain structure of quaternary ring; After the addition of HF, the template of AlPO-PIL2 2-D layered structure of AlPO-PIL2 was obtained by in-situ methylation of protonated 3-dimethylaminolprolamine during crystallization. 2. In the process of ionic thermal synthesis, two new aluminum phosphate materials, AlPO-PIL3 and AlPO-PIL4were obtained by using proton ionic liquid 3- diethylaminopropylamine acetate as solvent and template. The protonated 3-diethylaminopropylamine can transfer ethylated to form NHN-N-diethyl-1-N-propylenediamine, and then the 2-D layered AlPO-PIL3 with NNT-diethyl-3-propylenediamine as template is obtained. 3. The AlPO-PIL5 and AlPO-PIL6.CHN elemental analysis and TG-DSC analysis of two new structures obtained from proton type 3-dibutylaminopropylamine showed that there was no thermal decomposition in the crystallization process of the cation. The final entry into the aluminum phosphate skeleton plays the role of equilibrium skeleton charge. 4. Four kinds of aluminum phosphate materials: AlPO-PIL7AlPO-PIL8AlPO-PIL9 and AlPO-PIL10were synthesized in the proton N- N- tetramethylethylenediamine and NN- bis (3-aminopropyl) methylamine systems. Tetramethyl ethylenediamine cations located in the interlaminar equilibrium skeleton charge. AlPO-PIL9 is a one-dimensional chain structure formed by the connection of quaternary rings.
【學(xué)位授予單位】：太原理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：TQ133.1

【參考文獻】

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本文編號：1628239