【作者】 田野；

【导师】 闫文付；

【作者基本信息】 吉林大学 ， 无机化学， 2015， 硕士

【摘要】 沸石及相关的无机微孔晶体材料由于具有独特的孔道结构，在催化、吸附、分离以及离子交换等方面有着重要的应用。在这类材料的合成中，结构导向剂扮演了极其重要的角色。如果不使用结构导向剂，则得不到相应的微孔结构。影响结构导向剂发挥结构导向效应的因素很多，包括凝胶组成、原料的属性、结构导向剂的物理和化学属性、溶剂类型、晶化温度、时间以及矿化剂等。具有特定骨架结构以及特定性能的微孔材料的设计合成，是人们一直努力实现的目标，而这需要在分子层次上对这类材料的晶化机理以及晶化过程中的结构导向效应有清晰的认识。但到目前为止人们对这一问题的认识还十分有限，因此还需要在这方面继续开展研究，以认识结构导向效应的本质和来源。本论文致力于研究矿化剂氢氟酸(HF)在开放骨架磷酸铝合成中对有机胺结构导向效应的影响，取得了如下结果：1.研究了配比为Al2O3:4.0P2O5:3.0deta:153H2O和Al2O3:4.0P2O5:3.0deta:3.0HF:153H2O (deta为二乙烯三胺)的凝胶在180°C下的晶化过程。将晶化不同时间的产物用离心分离的方法进行固/液分离，采用XRD、NMR以及元素分析等方法对固相以及液相进行了表征。结果显示在初始凝胶中已经存在一些小结构单元，这些结构单元中的Al和P的配位态与最终产物中Al和P的配位态非常类似，但是两个体系中存在的小结构单元的类型和分布情况完全不同。这些小结构单元经历了不同的晶化过程，从而导致两种结构完全不同的磷酸铝开放骨架的生成。这两个合成体系的唯一区别在于是否加入HF。与不加HF的体系相比，添加HF体系的初始凝胶中就生成了含有氟离子的小结构单元，随着晶化的进行，氟离子进入到骨架中，最终生成了含氟的一维链状结构。因此，HF通过影响在晶化过程中生成的无机小结构单元的结构和分布来影响二乙烯三胺的结构导向效应。2.研究了配比为Al2O3:1.5P2O5:18.0en:147H2O和Al2O3:1.5P2O5:18.0en:3.0HF:147H2O (en为乙二胺)的凝胶在180°C下的晶化过程。将晶化不同时间的产物用离心分离的方法进行固/液分离，用XRD、元素分析等方法对固相以及液相产物进行表征。研究发现，氟化氢的引入显著改变了Al原子的配位状态，同时也影响了薄水铝石与磷酸之间的反应平衡、有机胺与磷酸之间的反应平衡，导致在不添加氟化氢的合成体系以及添加氟化氢的合成体系中，由薄水铝石和磷酸反应生成的磷酸铝小结构单元的种类和分布发生了显著变化，从而改变了两个合成体系的晶化方向，生成了两种拓扑结构完全不同的产物，表现为乙二胺结构导向效应发生了变化，氢氟酸对乙二胺结构导向效应产生了影响。这些结果表明有机胺的结构导向效应不仅取决于其自身的物理和化学性质，还受许多其它因素的影响。更多还原

【Abstract】 In the synthesis of zeolites and related materials with open-framework, thestructure-directing agent is the most important factor. It has been demonstrated that thestructure-directing effect can be affected by many factors. However, how these factorsaffect or determine the structure-directing effect remains unclear. The nature of thetemplate effect or the structure-directing effect is not yet clearly understood.In this thesis, we investigated the influence of the HF on the structure-directing effectof ethylenediamine (en) and diethylenetriamine (deta).The presence or absence of F-did have significant influence on the structure-directingeffect of ethylenediamine (en) and diethylenetriamine (deta) in the synthesis ofopen-framework aluminophosphates.1. In the absence of F-, a three-dimensional (3D) open-framework aluminophosphateAl4P5O20(H2O)2C4N3H16(AlPO-CJ31) was synthesized from the initial mixture with themolar composition of Al2O3:4.0P2O5:3.0deta:153H2O under hydrothermal condition,while a one-dimensional (1D) aluminophosphate Al2P4O10(OH)3F C4N3H15(ty-1) wascrystallized from the same initial mixture in the presence of F-(molar composition: Al2O3:4.0P2O5:3.0deta:3.0HF:153H2O). Their crystallization processes were characterizedby X-ray powder diffraction (XRD), solid-state magic-angle spinning nuclear magneticresonance (MAS NMR) and elemental analyses. The results show that the fluoride canaffect the structure-directing effect of diethylenetriamine by altering the type anddistribution of the fragments formed in the synthetic system and the starting point (coreunit) of the crystallization, which will determine the structure of the resulting crystals.2. For ethylenediamine, layered aluminophosphate Al2P2O9NH3(CH2)2NH3(UiO-13)can be obtained from the initial mixture with the molar composition of Al2O3:1.5P2O5:18.0en:147H2O under hydrothermal condition, while layered aluminophosphateAlF(HPO4)·NH2(CH2)2NH2(1) was obtained from the initial mixture with the same molarcomposition (Al2O3:1.5P2O5:18.0en:3.0HF:147H2O) with the exception of F-. Weinvestigated the crystallization processes of these two compounds by XRD and the evolution of the concentrations of Al and P in the liquid phases. The results show that thefluoride can affect the structure-directing effect of ethylenediamine by altering the type anddistribution of the fragments formed in the synthetic system and the starting point (coreunit) of the crystallization, which will determine the structure of the resulting crystals. Thestructural properties of open-framework aluminophosphates AlPO-CJ31, ty-1, UiO-13and1were analyzed in detail and the influence of the F-on the structure-directing effect ofdiethylenetriamine and ethylenediamine was discussed. The results show that the fluoridecan affect the structure-directing effect of diethylenetriamine by altering the type anddistribution of the fragments formed in the synthetic system and the starting point (coreunit) of the crystallization, which will determine the structure of the resulting crystals.更多还原