表面活性剂条件下硼酸镓的合成结构及性能研究

发布时间：2018-03-08 09:22

本文选题：硼酸镓　切入点：表面活性剂　出处：《浙江师范大学》2015年硕士论文　论文类型：学位论文

【摘要】：近几十年来,硼酸盐化合物在发光材料、非线性光学、催化和离子交换等领域的应用一直备受关注。硼具有BO3平面三角形和BO4四面体两种配位构型,BO3三角形和BO4四面体通过共顶点/边可以进一步形成三核至十八核的硼-氧簇。镓的外层电子结构与硼的相似,镓与氧可以形成GaO4、GaO5和GaO6等配位构型。GaOn多面体的引入,可以得到由硼-氧簇和镓-氧簇构筑的具有新颖结构的硼酸镓化合物。目前,已报道的硼酸镓是在高温固相、硼酸熔融及水热／溶剂热条件下合成出来,寻找新的合成方法对硼酸镓的合成研究具有极其重要的意义。本文用水热法合成了一例新型硼酸镓晶体：BaGa(B4O8)(OH)(H2O) (1)。在表面活性剂条件下合成了三例硼酸镓晶体：(2), (3), Na3GaB4O9 (4)。利用X-射线单晶衍射仪、X-射线粉末衍射、热重分析、红外吸收光谱、紫外-可见-近红外漫反射光谱、荧光光谱等测试方法对它们的结构及性质进行表征。化合物1结构中,GaB4O11(OH)簇与相邻的四个GaB4O11(OH)相连形成一个硼酸镓的层,两个相邻的层通过Ga-O键进一步连接形成三维孔层结构,Ba2+和游离水分子填充在层与层之间。该结构可简化为5-连接的拓扑结构,拓扑符号为(4862)。在370 nm光激发下,该化合物发蓝光,在473 nm处出现最强发射峰,荧光寿命为2.95 ns。化合物2的空间群为非中心对称的F43c。结构中,Ga6B4O24八面体笼与周围6个Ga6B4O24八面体笼连接形成三维孔道结构,Na+和OH-填充在孔道中。结构可简化为NaCl型拓扑结构,拓扑符号为(4966)。在277nm激发下,该化合物发绿光,在544m处出现最强发射峰,荧光寿命为22.65 ns。该化合物具有较弱的二阶非线性效应,SHG效应为0.1KDP。化合物3含有两种硼簇：{B3}簇与{B7}簇。一个{B3}簇与三个Ga04连接形成双链结构单元,一个{B7}簇与相邻的四个{B7}簇相连形成一个硼-氧层。双链结构单元与硼-氧层交替连接形成三维网络结构,Na+填充在空隙中。在274 nm光激发下,该化合物发绿光,在500 nm处出现最强发射峰,荧光寿命为28.44ns。化合物4结构中,一个GaO4四面体周围连接四个B4O8簇连接,一个B4O8簇周围连接四个GaO4四面体。GaO4四面体与B4O8簇交替连接形成二维褶皱层结构,Na+填充在层间间隙。在360 nm的激发波长下,该化合物发蓝光,在450nm处出现发射峰,荧光寿命为6.66 ns。以上工作进一步丰富了硼酸盐的合成及结构化学,为合成功能型硼酸盐提供了一条新的路径,对硼酸盐材料的进一步探索研究具有重要意义与价值。
[Abstract]:In recent decades, borates have grown in luminescent materials, nonlinear optics, The applications of catalysis and ion exchange have attracted much attention. Boron has two coordination configurations of BO3 plane triangle and BO4 tetrahedron, which can form tri-nucleus to 18 nucleus through covertex / edge. The electronic structure of the outer layer of gallium is similar to that of boron. Gallium and oxygen can form the coordination configuration of GaO4, GaO5 and GaO6, and the novel gallium borate compounds with novel structure can be obtained from boron oxide cluster and gallium oxide cluster. At present, gallium borate is reported to be a solid phase at high temperature. Boric acid was synthesized by melting and hydrothermal / solvothermal conditions. It is very important to find a new synthetic method for the synthesis of gallium borate. In this paper, a new type of gallium borate crystal: BaGaOB4O8OHH _ 2O) has been synthesized by hydrothermal method. Under the condition of surfactant, three cases of Gallium Borate crystals: w _ 2H _ 2, C _ 2O _ 3, Na3GaB4O9 _ 4H _ 2O have been synthesized. Using X-ray single crystal diffractometer, X-ray powder diffraction, Thermogravimetric Analysis, Infrared absorption Spectroscopy, UV-Vis / NIR diffuse Reflectance Spectroscopy, Their structures and properties were characterized by fluorescence spectroscopy. In compound 1, the GaB4O11OH cluster was connected with four adjacent GaB4O11OHs to form a layer of gallium borate. The two adjacent layers are further connected by Ga-O bond to form a three-dimensional porous layer structure, Ba2 and free water molecules are filled between layers. The structure can be simplified as a 5-connected topological structure with a topological symbol of 48,862. Under the excitation of 370nm light, the compound emits blue light. The strongest emission peak appears at 473 nm. The fluorescence lifetime of compound 2 is 2.95 ns.The space group of compound 2 is a non-centrosymmetric F43c. In the structure, Ga6B4O24 octahedron cage is connected with the surrounding six Ga6B4O24 octahedral cages to form a three-dimensional pore structure, Na and OH- filled in the pore channel. The structure can be simplified as a NaCl topological structure. The topological symbol is 4966nm. under the excitation of 277nm, the compound has green light and the strongest emission peak appears at 544m. The fluorescence lifetime of the compound is 22.65 ns.The second order nonlinear effect of the compound is 0.1KDP.The compound 3 contains two kinds of boron clusters: {B3} cluster and {B7} cluster. One {B3} cluster joins with three Ga04 to form a double-stranded structure unit. A {B7} cluster is connected with four adjacent {B7} clusters to form a boron-oxygen layer. The double chain structure unit interconnects with the boron-oxygen layer alternately to form a three-dimensional network structure Na filled in the void. Under 274 nm light excitation, the compound has green light. The strongest emission peak appeared at 500nm, and the fluorescence lifetime was 28.44ns.In compound 4, four B _ 4O _ 8 clusters were connected around a GaO4 tetrahedron. Four GaO4 tetrahedra 路GaO4 tetrahedron and B _ 4O _ 8 cluster are connected around a B _ 4O _ 8 cluster alternately to form a two-dimensional folded layer structure and Na filled in the interlaminar gap. At the excitation wavelength of 360nm, the compound emits blue light with emission peaks at 450 nm. The fluorescence lifetime is 6.66 ns. The above work further enriches the synthesis and structural chemistry of borates, and provides a new route for the synthesis of functional borates, which is of great significance and value for the further exploration and study of borate materials.
【学位授予单位】：浙江师范大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TQ133.51

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