本文選題：硼酸鎵　切入點：表面活性劑　出處：《浙江師范大學》2015年碩士論文　論文類型：學位論文

【摘要】：近幾十年來,硼酸鹽化合物在發(fā)光材料、非線性光學、催化和離子交換等領(lǐng)域的應用一直備受關(guān)注。硼具有BO3平面三角形和BO4四面體兩種配位構(gòu)型,BO3三角形和BO4四面體通過共頂點/邊可以進一步形成三核至十八核的硼-氧簇。鎵的外層電子結(jié)構(gòu)與硼的相似,鎵與氧可以形成GaO4、GaO5和GaO6等配位構(gòu)型。GaOn多面體的引入,可以得到由硼-氧簇和鎵-氧簇構(gòu)筑的具有新穎結(jié)構(gòu)的硼酸鎵化合物。目前,已報道的硼酸鎵是在高溫固相、硼酸熔融及水熱／溶劑熱條件下合成出來,尋找新的合成方法對硼酸鎵的合成研究具有極其重要的意義。本文用水熱法合成了一例新型硼酸鎵晶體：BaGa(B4O8)(OH)(H2O) (1)。在表面活性劑條件下合成了三例硼酸鎵晶體：(2), (3), Na3GaB4O9 (4)。利用X-射線單晶衍射儀、X-射線粉末衍射、熱重分析、紅外吸收光譜、紫外-可見-近紅外漫反射光譜、熒光光譜等測試方法對它們的結(jié)構(gòu)及性質(zhì)進行表征�；衔�1結(jié)構(gòu)中,GaB4O11(OH)簇與相鄰的四個GaB4O11(OH)相連形成一個硼酸鎵的層,兩個相鄰的層通過Ga-O鍵進一步連接形成三維孔層結(jié)構(gòu),Ba2+和游離水分子填充在層與層之間。該結(jié)構(gòu)可簡化為5-連接的拓撲結(jié)構(gòu),拓撲符號為(4862)。在370 nm光激發(fā)下,該化合物發(fā)藍光,在473 nm處出現(xiàn)最強發(fā)射峰,熒光壽命為2.95 ns�；衔�2的空間群為非中心對稱的F43c。結(jié)構(gòu)中,Ga6B4O24八面體籠與周圍6個Ga6B4O24八面體籠連接形成三維孔道結(jié)構(gòu),Na+和OH-填充在孔道中。結(jié)構(gòu)可簡化為NaCl型拓撲結(jié)構(gòu),拓撲符號為(4966)。在277nm激發(fā)下,該化合物發(fā)綠光,在544m處出現(xiàn)最強發(fā)射峰,熒光壽命為22.65 ns。該化合物具有較弱的二階非線性效應,SHG效應為0.1KDP�；衔�3含有兩種硼簇：{B3}簇與{B7}簇。一個{B3}簇與三個Ga04連接形成雙鏈結(jié)構(gòu)單元,一個{B7}簇與相鄰的四個{B7}簇相連形成一個硼-氧層。雙鏈結(jié)構(gòu)單元與硼-氧層交替連接形成三維網(wǎng)絡(luò)結(jié)構(gòu),Na+填充在空隙中。在274 nm光激發(fā)下,該化合物發(fā)綠光,在500 nm處出現(xiàn)最強發(fā)射峰,熒光壽命為28.44ns�；衔�4結(jié)構(gòu)中,一個GaO4四面體周圍連接四個B4O8簇連接,一個B4O8簇周圍連接四個GaO4四面體。GaO4四面體與B4O8簇交替連接形成二維褶皺層結(jié)構(gòu),Na+填充在層間間隙。在360 nm的激發(fā)波長下,該化合物發(fā)藍光,在450nm處出現(xiàn)發(fā)射峰,熒光壽命為6.66 ns。以上工作進一步豐富了硼酸鹽的合成及結(jié)構(gòu)化學,為合成功能型硼酸鹽提供了一條新的路徑,對硼酸鹽材料的進一步探索研究具有重要意義與價值。
[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.
【學位授予單位】：浙江師范大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：TQ133.51

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