质子型离子液体中磷酸铝骨架材料的合成及结构表征

发布时间：2018-03-18 05:31

本文选题：离子热合成　切入点：质子型离子液体　出处：《太原理工大学》2015年硕士论文　论文类型：学位论文

【摘要】：磷酸铝多孔材料作为分子筛的一大类，在催化、吸附及分离等方面具有潜在的应用价值，设计和合成具有新型结构的磷酸铝材料具有重要的意义。目前，大部分磷酸铝材料都是在有机胺存在的条件下，通过水热或溶剂热途径合成的，溶剂和有机胺模板剂是影响磷酸铝骨架结构的重要因素。离子热合成法，利用离子液体作为溶剂和模板剂，在新型无机多孔材料的合成方面显示出独特的优势。质子型离子液体作为离子液体的一个分支，它是通过Br nsted酸和Br nsted碱之间质子化转移反应形成的，，和传统的离子液体相比，具有价格便宜、易于提纯等优势。论文采用乙酸对有机胺进行质子化，得到五种质子型离子液体，并用五种质子型离子液体作为溶剂和模板剂，研究了新型磷酸铝材料的合成特点和规律。通过改变合成条件合成出十种磷酸铝材料，利用XRD、NMR、TG-DSC、SEM、CHN元素分析等方法对样品的结构及物化性质进行了表征，主要研究内容和结论如下： 1、在质子型的3-二甲胺基丙胺离子液体中得到两种磷酸铝材料AlPO-PIL1和AlPO-PIL2，HF对相的选择性起到重要的作用。无HF时，得到的AlPO-PIL1具有一维链状四元环结构；加入HF后得到AlPO-PIL2二维层状结构，AlPO-PIL2的模板剂N,N'-二甲基-1,3-丙二胺是在晶化的过程中，质子化的3-二甲胺基丙胺发生分子内原位甲基转移得到。 2、在离子热合成中，以质子型的离子液体3-二乙胺基丙胺乙酸盐作为溶剂和模板剂，得到两种新型结构的磷酸铝材料，AlPO-PIL3和AlPO-PIL4。单晶结构解析发现：在晶化过程中，质子化的3-二乙胺基丙胺会发生乙基化转移生成N,N'-二乙基-1,3-丙二胺，进而得到以N,N'-二乙基-1,3-丙二胺为模板剂的二维层状结构的AlPO-PIL3。 3、在质子型的3-二丁胺基丙胺中得到的两种具有新型结构的AlPO-PIL5和AlPO-PIL6。CHN元素分析和TG-DSC分析表明：3-二丁氨基丙胺阳离子在晶化的过程中没有发生热分解，最终进入到磷酸铝骨架中起到平衡骨架电荷的作用。 4、在质子型的N,N-四甲基乙二胺和N,N-双(3-氨丙基)甲胺体系中共合成了四种磷酸铝材料：AlPO-PIL7、AlPO-PIL8、AlPO-PIL9和AlPO-PIL10。通过单晶结构解析得到了两种材料的结构，AlPO-PIL7为二维层状结构，四甲基乙二胺阳离子位于层间平衡骨架电荷。AlPO-PIL9是由四元环连接而成的一维链状结构。
[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.
【学位授予单位】：太原理工大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TQ133.1

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