金属磷（膦）酸盐的水热合成、结构与性质研究
发布时间：2018-08-22 16:19
【摘要】：微孔材料化合物由于其丰富的化学结构以及在催化、分离、离子交换、吸附及光学性质等方面的潜在应用引起了人们广泛的研究。本论文通过调控反应条件(温度,压强,反应时间等)、磷源(磷酸,亚磷酸,有机膦酸)、金属离子以及作为结构导向剂的有机胺,通过在水热合成的方法,实现微孔金属磷(膦)酸盐化合物的多样化自组装。结合单晶X-射线衍射、红外光谱分析、热重、元素分析、荧光光谱、质子导电、磁性等性质研究对合成的晶体表征。论文具体工作如下:一、在水热合成的条件下,选取磷酸为主体,在水-甲醇溶剂中,引入不同类型的含N杂环有机胺作为配体,实现了原位甲基化转化。合成了三例通过原位生成模板剂(N,N,N’,N’-4-甲基哌嗪,N,N,-二甲基-1,4-二氮杂环[2,2,2])诱导下的新型金属磷酸铝化合物:[dmdabco][Al_2(HPO_4)_4](3-1)、[tmpip]_(0.5)[Al(HPO_4)_2](3-2)、[tmpip][Al_6(PO_4)_6(HPO_4)]?(H_2O)(3-3)。其中,化合物3-1和3-2是两例同构的,具有一维链结构的金属磷酸铝化合物;化合物3-3是一例少见的P/Al比为6/7的三维开放骨架结构化合物,其结构由AlO_4,AlO_5,PO_4和HPO_4四面体单元构成。二、在水热合成条件下,选取亚磷酸为主体,在不同有机胺模板剂的诱导下合成三例具有新颖结构的亚磷酸锌化合物:[Hapy]_2[Zn_3(HPO_3)_4](3-4)[H_2hepip][Zn_3(HPO_3)_4](H_2O)_(0.25)(3-5)[H_2tmdab][Zn_3(HPO_3)_4](3-6)。三例化合物均由3-连接的HPO_3和4-连接的ZnO_4共顶点形成含有12-元环的亚磷酸锌三维结构化合物,其中,化合物3-6结构中含有左右手螺旋链。三、在水热合成条件下,以有机膦(羟基乙叉二膦酸或氨基三亚甲基磷酸)为主体,引入刚性的环状有机胺,得到三例结构新颖的过渡金属有机膦酸盐:[Zn_3{N(CH_2 PO3)3}(TIB)]·8H_2O(4-1),[Co3{N(CH_2 PO3)3}(TIB)]·9H_2O(4-2),[H_3TPT][Zn_3CH_3C(O)(PO3)2)]CH_3C(O)(PO3)2H)]·(H_2O)(4-3)。其中,化合物4-1和4-2是两例同构的、具有三维层-柱结构,层与层之间由有机配体作为柱撑结构,分别具有荧光性质及磁性;化合物4-3是一例由金属离子与有机膦配位构成的二维层状结构化合物,值得注意的是该化合物具有光致/热致可逆变色性质。
[Abstract]:Due to their rich chemical structure and potential applications in catalysis, separation, ion exchange, adsorption and optical properties, microporous materials have been widely studied. In this paper, by regulating reaction conditions (temperature, pressure, reaction time, etc.), phosphorous sources (phosphoric acid, phosphorous acid, organic phosphonic acid), metal ions and organic amines as structural guidance agents, the method of hydrothermal synthesis was used. The multiplex self-assembly of microporous phosphorus (phosphine) acid compounds was realized. The synthesized crystals were characterized by X-ray diffraction, infrared spectroscopy, thermogravimetry, elemental analysis, fluorescence spectroscopy, proton conduction and magnetic properties. The main work of this paper is as follows: firstly, under the condition of hydrothermal synthesis, phosphoric acid was selected as the main body, and different kinds of heterocyclic organic amines containing N were introduced as ligands in water-methanol solvent to realize in situ methylation conversion. Three new metal aluminophosphate compounds induced by in situ formation of template (NNN, N, N, N, O, N, N, N, N, N, N, P, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, P, N, N, N, N, N, N, N, N, N, N, N, P, N, N, N, N, N, N, N, N, N, N, N, N, P, N, N, N, N Compounds 3-1 and 3-2 are two isomorphic metal aluminophosphate compounds with one-dimensional chain structure, and compound 3-3 is a rare three-dimension open skeleton structure compound with P/Al ratio of 6 / 7. The structure of compound 3-2 is composed of AlOSP _ 4O _ 5O _ 5PO _ 4 and HPO_4 tetrahedron unit. Secondly, three novel zinc phosphite compounds with novel structure were synthesized by hydrothermal synthesis with phosphorous acid as the main body and induced by different organic amine templates: [Hapy] 2 [Zn_3 (HPO_3) 4] (3-4) [H_2hepip] [Zn_3 (HPO_3) 4] (H _ 2O) _ (0.25) (3-5) [H_2tmdab] [Zn_3 (HPO_3) _ 4] (3-6). In the three cases, the 3-linked HPO_3 and the 4-connected ZnO_4 co-apex to form the three-dimensional structure compound of zinc phosphite containing 12-member ring. The structure of compound 3-6 contains the left and right hand helical chain. 涓，
本文编号：2197647
[Abstract]:Due to their rich chemical structure and potential applications in catalysis, separation, ion exchange, adsorption and optical properties, microporous materials have been widely studied. In this paper, by regulating reaction conditions (temperature, pressure, reaction time, etc.), phosphorous sources (phosphoric acid, phosphorous acid, organic phosphonic acid), metal ions and organic amines as structural guidance agents, the method of hydrothermal synthesis was used. The multiplex self-assembly of microporous phosphorus (phosphine) acid compounds was realized. The synthesized crystals were characterized by X-ray diffraction, infrared spectroscopy, thermogravimetry, elemental analysis, fluorescence spectroscopy, proton conduction and magnetic properties. The main work of this paper is as follows: firstly, under the condition of hydrothermal synthesis, phosphoric acid was selected as the main body, and different kinds of heterocyclic organic amines containing N were introduced as ligands in water-methanol solvent to realize in situ methylation conversion. Three new metal aluminophosphate compounds induced by in situ formation of template (NNN, N, N, N, O, N, N, N, N, N, N, P, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, P, N, N, N, N, N, N, N, N, N, N, N, P, N, N, N, N, N, N, N, N, N, N, N, N, P, N, N, N, N Compounds 3-1 and 3-2 are two isomorphic metal aluminophosphate compounds with one-dimensional chain structure, and compound 3-3 is a rare three-dimension open skeleton structure compound with P/Al ratio of 6 / 7. The structure of compound 3-2 is composed of AlOSP _ 4O _ 5O _ 5PO _ 4 and HPO_4 tetrahedron unit. Secondly, three novel zinc phosphite compounds with novel structure were synthesized by hydrothermal synthesis with phosphorous acid as the main body and induced by different organic amine templates: [Hapy] 2 [Zn_3 (HPO_3) 4] (3-4) [H_2hepip] [Zn_3 (HPO_3) 4] (H _ 2O) _ (0.25) (3-5) [H_2tmdab] [Zn_3 (HPO_3) _ 4] (3-6). In the three cases, the 3-linked HPO_3 and the 4-connected ZnO_4 co-apex to form the three-dimensional structure compound of zinc phosphite containing 12-member ring. The structure of compound 3-6 contains the left and right hand helical chain. 涓，
本文编号：2197647
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