金属（亚）磷酸盐的水热合成、晶体结构及性质研究
发布时间：2018-07-24 15:24
【摘要】：微孔材料化合物由于其丰富的化学组成以及在催化、气体储藏、吸附、分离等方面的潜在应用引起了人们极大的研究兴趣。本论文通过直接选取不同有机胺作为配体或采用模板剂的“原位”设计与合成策略,在水热条件下实现微孔金属(亚)磷酸盐化合物的多样化组装。通过单晶X-射线衍射、元素分析、红外光谱、粉末X-射线衍射、热重、荧光等对合成晶体化合物进行结构表征与性质测试。论文具体工作如下:1、在水热条件下,选取不同类型的柔性链状有机胺、含N杂环有机胺作为配体,合成了四例新型的有机-无机杂化(亚)磷酸锌化合物:[C6N2O2H16][Zn(HPO3)]2(3-1)、(NH4)[Zn5(PO4)3(HPO4)2(HAPIM)2]·(H2O)(3-2)、[Hampy][Zn2(HPO3)(PO4)](3-3)、[ampy][Zn2(HPO3)](3-4)。其中,化合物3-1是一例以柔性线型有机配体作为柱撑结构的有机-无机杂化亚磷酸锌化合物;化合物3-2、3-3、3-4是以含N杂环有机胺作为配体合成的。化合物3-2是一例含16-元环超大孔道结构的磷酸锌化合物;化合物3-3是一例具有二维层结构的磷酸-亚磷酸锌化合物,且具有荧光及光致变色性质;化合物3-2和化合物3-3的合成中,有机胺不仅作为配体参与了骨架的构建,而且还起到了结构导向剂的作用;化合物3-4的空间结构是由中性亚磷酸锌层通过刚性含N杂环有机配体柱撑而成。2、水热条件下,在水-甲醇介质中,实现了系列脂肪族有机胺及芳香族有机胺的原位甲基化转化,包含1,4-二氮杂环[2,2,2]辛烷、哌嗪、1,4-二甲基哌嗪、2,6-二甲基哌嗪、3-氨甲基吡啶、吡啶、4,4’-联吡啶;并分别在原位生成模板剂N,N’-二甲基-1,4二氮杂环[2,2,2]辛烷、N,N,N’,N’-四甲基哌嗪、N-甲基-2,6-二甲基哌嗪、N-甲基吡啶、N,N’-二甲基-4,4’-联吡啶的诱导下合成了14例新颖金属(亚)磷酸盐化合物,包括四例不同维数的磷酸铍化合物(化合物4-1~4-4),四例磷酸镓化合物(化合物4-5~4-8),三例不同结构特点的磷酸锌化合物(化合物4-9~4-11)以及三例亚磷酸锌化合物(化合物4-12~4-14)。
[Abstract]:Due to their rich chemical composition and potential applications in catalysis, gas storage, adsorption and separation, microporous materials have attracted much attention. In this paper, by selecting different organic amines as ligands or adopting "in situ" design and synthesis strategy of template, we can realize the diversified assembly of microporous metal (hypophosphite) compounds under hydrothermal conditions. The structure and properties of the synthesized crystal compounds were characterized by single crystal X-ray diffraction, elemental analysis, infrared spectroscopy, powder X-ray diffraction, thermogravimetry and fluorescence. In this paper, four novel organic-inorganic hybrid (C6N2O2H16) zinc phosphate compounds, [C6N2O2H16] [Zn (HPO3)] 2 (3-1), (NH4) [Zn5 (PO4) 3 (HPO4) 2 (HAPIM) 2] (H2O) (3-2), [Hampy] [Zn2 (HPO3) (PO4)] (3-3), [ampy] [Zn2 (HPO3)] (3-4) were synthesized by using different types of flexible chain organic amines and N heterocyclic organic amines as ligands under hydrothermal conditions as follows: [C6N2O2H16] [Zn (HPO3)] 2 (3-1), (NH4) [Zn5 (PO4) 3 (HPO4) 2 (HAPIM) 2] (H2O) (3-2), [Hampy] [Zn2 (HPO3) (PO4)] (3-3), [ampy] [Zn2 (HPO3)] (3-4). Compound 3-1 is an organic-inorganic hybrid zinc phosphite compound with flexible linear organic ligands as pillared structure, and compound 3-2C3-3Phosphite 3-4 is synthesized from N-containing heterocyclic organic amines as ligands. Compound 3-2 is a zinc phosphate compound with a large pore structure of 16-unit ring, compound 3-3 is a two-dimension structure of zinc phosphate-phosphite compound, and it has fluorescence and photochromic properties. In the synthesis of compound 3-2 and compound 3-3, organic amines not only participate in the construction of framework as ligands, but also act as structural guidance agents. The spatial structure of compound 3-4 is composed of neutral zinc phosphite layer supported by rigid heterocyclic organic ligands containing N. The in situ methylation of aliphatic organic amines and aromatic organic amines is realized in aqueous and methanol medium under hydrothermal conditions. It contains 1: 4- diaza-heterocyclic [2o _ 2o _ 2] octane, piperazine (1-dimethylpiperazine), 2-dimethyl-piperazine (2-dimethylpiperazine), 3-aminomethylpyridine (3-aminomethylpyridine), 4zapyridine, bipyridine; The synthesis of 14 cases of pyridine was carried out under the induction of in situ synthesis of the template agent NHN, dimethyl, diazocyclic [2, 2, n, 2] octanohexane, N, N-, tetramethyl, piperazine, N-, methyl-2, dimethyl, piperazine, and dimethylpyridine, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, Novel Metallic (sulfite) Phosphate compounds, It consists of four beryllium phosphate compounds (compounds 4-1n 4-4), four gallium phosphate compounds (compounds 4-54-8), three zinc phosphate compounds with different structural characteristics (compound 4-9nc-11) and three zinc phosphite compounds (compound 4-124-14).
【学位授予单位】：青岛大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB383.4;O611.4
本文编号：2141812
[Abstract]:Due to their rich chemical composition and potential applications in catalysis, gas storage, adsorption and separation, microporous materials have attracted much attention. In this paper, by selecting different organic amines as ligands or adopting "in situ" design and synthesis strategy of template, we can realize the diversified assembly of microporous metal (hypophosphite) compounds under hydrothermal conditions. The structure and properties of the synthesized crystal compounds were characterized by single crystal X-ray diffraction, elemental analysis, infrared spectroscopy, powder X-ray diffraction, thermogravimetry and fluorescence. In this paper, four novel organic-inorganic hybrid (C6N2O2H16) zinc phosphate compounds, [C6N2O2H16] [Zn (HPO3)] 2 (3-1), (NH4) [Zn5 (PO4) 3 (HPO4) 2 (HAPIM) 2] (H2O) (3-2), [Hampy] [Zn2 (HPO3) (PO4)] (3-3), [ampy] [Zn2 (HPO3)] (3-4) were synthesized by using different types of flexible chain organic amines and N heterocyclic organic amines as ligands under hydrothermal conditions as follows: [C6N2O2H16] [Zn (HPO3)] 2 (3-1), (NH4) [Zn5 (PO4) 3 (HPO4) 2 (HAPIM) 2] (H2O) (3-2), [Hampy] [Zn2 (HPO3) (PO4)] (3-3), [ampy] [Zn2 (HPO3)] (3-4). Compound 3-1 is an organic-inorganic hybrid zinc phosphite compound with flexible linear organic ligands as pillared structure, and compound 3-2C3-3Phosphite 3-4 is synthesized from N-containing heterocyclic organic amines as ligands. Compound 3-2 is a zinc phosphate compound with a large pore structure of 16-unit ring, compound 3-3 is a two-dimension structure of zinc phosphate-phosphite compound, and it has fluorescence and photochromic properties. In the synthesis of compound 3-2 and compound 3-3, organic amines not only participate in the construction of framework as ligands, but also act as structural guidance agents. The spatial structure of compound 3-4 is composed of neutral zinc phosphite layer supported by rigid heterocyclic organic ligands containing N. The in situ methylation of aliphatic organic amines and aromatic organic amines is realized in aqueous and methanol medium under hydrothermal conditions. It contains 1: 4- diaza-heterocyclic [2o _ 2o _ 2] octane, piperazine (1-dimethylpiperazine), 2-dimethyl-piperazine (2-dimethylpiperazine), 3-aminomethylpyridine (3-aminomethylpyridine), 4zapyridine, bipyridine; The synthesis of 14 cases of pyridine was carried out under the induction of in situ synthesis of the template agent NHN, dimethyl, diazocyclic [2, 2, n, 2] octanohexane, N, N-, tetramethyl, piperazine, N-, methyl-2, dimethyl, piperazine, and dimethylpyridine, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, Novel Metallic (sulfite) Phosphate compounds, It consists of four beryllium phosphate compounds (compounds 4-1n 4-4), four gallium phosphate compounds (compounds 4-54-8), three zinc phosphate compounds with different structural characteristics (compound 4-9nc-11) and three zinc phosphite compounds (compound 4-124-14).
【学位授予单位】：青岛大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB383.4;O611.4
【共引文献】
相关博士学位论文 前5条
1 何永科;开放骨架磷酸/亚磷酸锰、硼磷酸锰的离子热合成[D];吉林大学;2014年
2 王学雷;新型开放骨架亚磷酸盐晶体的合成、结构与性质表征[D];吉林大学;2014年
3 吴俊标;新型光致变色无机开放骨架晶体材料的合成、结构与性质[D];吉林大学;2015年
4 卢慧英;开放骨架磷酸铝的合成及乙二胺分子的结构导向效应研究[D];吉林大学;2015年
5 刘威;稀土微孔晶体材料的高温高压合成及荧光性质的研究[D];吉林大学;2015年
相关硕士学位论文 前1条
1 李欣洁;含硼离子液体的合成、表征及其在硼磷酸盐合成中的应用[D];东北大学;2012年
，本文编号：2141812
本文链接：https://www.wllwen.com/kejilunwen/cailiaohuaxuelunwen/2141812.html
