高溫高壓水熱法合成鹼土金屬硼酸鹽及其結構研究;High-Temperature, High-Pressure Hydrothermal Synthesis and Structural Study of Alkaline Earth Metal Borates

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题名:	高溫高壓水熱法合成鹼土金屬硼酸鹽及其結構研究;High-Temperature, High-Pressure Hydrothermal Synthesis and Structural Study of Alkaline Earth Metal Borates
作者:	李宜璋;Lee, Yi-Chang
贡献者:	化學學系
关键词:	高溫高壓水熱法;硼酸;非線性光學;二次倍頻;鹼土金屬;High-Temperature;High-Pressure;Hydrothermal Synthesis;Alkaline Earth Metal;Borates;nonlinear optical
日期:	2018-07-30
上传时间:	2018-08-31 11:34:09 (UTC+8)
出版者:	國立中央大學
摘要:	本論文以高溫高壓水熱法合成三個鹼土金屬硼酸鹽Ba3B10O17(OH)2 (BB1)、Ba2B5O9(OH) (BB2)及Sr2.5Na0.5H0.5B6O11(OH)2·0.33H2O (SNB1)。藉由單晶X光繞射方法，鑑定出化合物的晶體結構，再以粉末X光繞射分析比對理論圖，確定樣品純度。用X光能量散布分析儀確定SNB1有鈉及鍶的存在，用紅外線光譜儀確認BB1的OH基，並以倍頻訊號測量測得BB1的粉末二次倍頻訊號為SiO2的一半。 BB1為二維雙層結構，基本建構單元用化簡符號寫為4∆6□: 2[<∆2□>-<∆2□>]，其利用共氧的共角方式連結在ab平面無限延伸形成雙層，Ba2+陽離子則座落在層內的九圓環與層間穩定結構。而BB2為二維單層結構，基本建構單元寫為2∆3□: <∆2□>-<∆2□>，以共氧的共角方式連結向a軸無限延伸，再以一上一下的鋸齒狀排列成層，此層再利用反轉中心，形成另一層並彼此穿插疊合，Ba2+陽離子則座落在層內的九圓環與層間穩定結構。化合物SNB1為一維鏈狀結構，基本建構單元寫為2∆4□: ∆<3□>-<∆2□>，其藉著沿a軸延伸，組成三個硼氧六圓環並無限排列形成單鏈，單鏈再透過反轉中心，形成上下相反的鏈並在空間中無限延伸，Sr2+與Na+陽離子在鏈與鏈之間穩定結構。與文獻中的化合物比較，利用高溫高壓水熱合成法可調整硼酸鹽結構，合成具潛力的新型非線性光學材料。 ;Three new alkaline earth borates, Ba3B10O17(OH)2 (BB1), Ba2B5O9(OH) (BB2) and Sr2.5Na0.5H0.5B6O11(OH)2·0.33H2O (SNB1), were synthesized by the high-temperature, high-pressure hydrothermal method, and their crystal structures were determined by single crystal X-ray diffraction, and further characterized by EDS, IR, and SHG. BB1 has a two-dimensional double-layer structure. The fundamental building block (FBB) is a decaborate group formed by six nonequivalent BO4 tetrahedra and four BO3 triangles. The descriptor of the FBB is 4∆6□: 2[<∆2□>- <∆2□>]. The FBBs are connected by sharing oxygen corners to form twodimensional double layers. Ba2+ cations are located at sites in the intralayer and interlayer regions. BB2 has a two-dimensional single-layer structure. The FBBs which can be written as 2∆3□: <∆2□>-<∆2□> are connected by sharing oxygen corners to form an infinite chain. The chains are further interconnected to result in a zigzag layer with the Ba2+ cations being located in the intralayer and interlayer regions. SNB1 has a one-dimensional chain structure. The descriptor of the FBB is 2∆4□: ∆<3□>-<∆2□>, which contains three hexagonal B-O rings. The FBBs are connected by sharing oxygen corners to form infinite chains and there are two chains per unit cell which are related by an inversion center. These three borate compounds are compared with those in the literature. The high-temperature, highpressure hydrothermal reaction is a versatile method to synthesize new borate materials for NLO applications.
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