高溫高壓水熱法合成鹼土金屬硼酸鹽及其結構研究

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李宜璋(Yi-Chang Lee) 查詢紙本館藏

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化學學系

論文名稱

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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摘要(中)

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[-]，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□: -，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□>-，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。

摘要(英)

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[-
]. 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□: - 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□>-, 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.

關鍵字(中)

★ 高溫高壓水熱法
★ 硼酸
★ 非線性光學
★ 二次倍頻
★ 鹼土金屬

關鍵字(英)

★ High-Temperature
★ High-Pressure
★ Hydrothermal Synthesis
★ Alkaline Earth Metal
★ Borates
★ nonlinear optical

論文目次

摘要 i
Abstract ii
謝誌 iii
目錄 iv
圖目錄 vii
表目錄 x
第1章緒論 1
1-1 雷射 1
1-1-1 雷射的原理與歷史 1
1-1-2 雷射的分類 3
1-2 非線性光學 4
1-2-1 非線性光學的原理與歷史 4
1-2-2 非線性光學晶體及其應用 5
1-3 硼酸鹽 13
1-3-1 硼酸鹽非線性光學發展 15
1-4 論文研究動機 17
1-5 研究成果摘要 18
第2章實驗與結構解析 19
2-1 合成方法 19
2-1-1 水熱法 19
2-1-2 使用設備清單 21
2-1-3 使用藥品清單 22
2-2 鑑定方法 23
2-2-1 使用儀器列表 23
2-2-2 單晶X光繞射儀與結構分析 25
2-2-3 粉末X光繞射儀 (PXRD) 31
2-2-4 X光能量散佈分析儀 (EDS) 32
2-2-5 紅外線光譜儀 (IR) 33
2-2-6 倍頻訊號測量 (SHG) 34
2-3 高溫高壓水熱合成 35
2-3-1 Ba3B10O17(OH)2 (BB1) 合成條件 35
2-3-2 Ba2B5O9(OH) (BB2) 合成條件 37
2-3-3 Sr2.5Na0.5H0.5B6O11(OH)2·0.33H2O (SNB1) 合成條件 38
2-4 單晶X光繞射結構解析 38
2-4-1 單晶X光繞射分析 38
2-4-2 Ba3B10O17(OH)2 (BB1) 結構解析 40
2-4-3 Ba2B5O9(OH) (BB2) 結構解析 42
2-4-4 Sr2.5Na0.5H0.5B6O11(OH)2·0.33H2O (SNB1) 結構解析 44
2-5 化合物鑑定與性質測量 46
2-5-1 Ba3B10O17(OH)2 粉末X光繞射分析 46
2-5-2 Ba3B10O17(OH)2 紅外線光譜分析 48
2-5-3 Ba3B10O17(OH)2 倍頻訊號測量 49
2-5-4 Sr2.5Na0.5H0.5B6O11(OH)2·0.33H2O X光能量散佈光譜分析 50
第3章結果與討論 51
3-1 晶體結構描述 51
3-1-1 Ba3B10O17(OH)2 (BB1) 結構描述 51
3-1-2 Ba2B5O9(OH) (BB2) 結構描述 55
3-1-3 Sr2.5Na0.5H0.5B6O11(OH)2·0.33H2O (SNB1) 結構描述 58
3-2 結果與討論 62
3-2-1 Ba3B10O17(OH)2 (BB1) 結構比較與討論 62
3-2-2 Ba2B5O9(OH) (BB2) 結構比較 66
3-2-3 Sr2.5Na0.5H0.5B6O11(OH)2·0.33H2O (SNB1) 結構比較 70
第4章結論 74
參考文獻 76
附錄 79

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指導教授

李光華(Kwang-Hwa Lii)

審核日期

2018-7-30

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