臺灣博碩士論文加值系統

本論文利用高溫高壓水熱合成法與助熔劑長晶法合成了十個具有新穎結構的稀土元素與錒系矽酸鹽結構，其中四個稀土鎵矽酸鹽為等結構化合物，加上不同價數之鈾矽酸鹽總共分為三個系列加以介紹。所得化合物皆以單晶X光繞射方法收集數據後進行結構解析，再藉由調整合成方法以得到化合物的純相抑或是主要產物。利用粉末X光繞射圖譜與理論圖譜做比對以確定樣品純度供後續物理性質的測量。進行變溫粉末繞射實驗以確定結構之熱穩定度，並以固態核磁共振光譜、X光光電子光譜與X光吸收光譜來獲得化合物進一步資訊與單晶數據做驗證。再針對不同化合物的特性作量測: 例如以光致發光光譜、發光生命期量測以及其放光色度座標來了解化合物發光的特性；倍頻訊號量測佐證非中心對稱結構的存在。

第一個系列主要介紹一個新穎之稀土元素鎵矽酸鹽，主要是由[GaSi4O12]的混離子雙層與REO7多面體共邊形成之一維無限鏈所組成。此結構分別可以得到釔、銪、釓與鋱等四種稀土金屬之等結構，也可以將銪與鋱單獨或同時摻雜入以釔為主體之結構，這些具有發光特性之結構可以用來作為新穎螢光粉的應用。

第二個系列則是選擇不同之助熔劑組合來得到六價鈾矽酸鹽結構，B1與B2結構中不僅有鹽類分子存在且形成十二員環的大孔洞。B3化合物則是具有新穎連接方式之[Si8O22]12-與被隔開之Urφ4雙四角錐組合而成。

第三個系列是以高溫高壓水熱法得到兩個混價鈾矽酸鹽結構，合成配比中各加入兩種鹼金族陽離子以及氟離子，氟離子可以幫助得到還原態之鈾矽酸鹽，而雙陽離子同時進入結構中可能是產生混價結構之原因。C2結構中則是同時具有UIVO6、UVO7與UV/VIO7三種具有不同價數的結晶學位置的鈾。XPS以及XANES提供了有力的證據來證實結構中不同價數成份的存在。

This thesis introduces ten new rare-earth and uranium silicates which were synthesized by high-temperature, high-pressure hydrothermal or flux-growth methods. Four rare-earth gallosilicates adopt the same structural type and uranium silicates are classified into two series based on their valences. All structures were characterized by single crystal X-ray diffraction (SXRD). Pure or major phase of products can be obtained by adjusting experiment conditions. Their purities were checked by powder X-ray diffraction. The variable temperature powder diffraction patterns were used to understand the thermal stability of the compounds. Solid state NMR, X-ray photoelectron spectroscopy and X-ray absorption spectroscopy can give us structural information as compared with that from SXRD. Characterizations including photoluminescence, emission life time and second-harmonic generation were measured to investigate interesting properties of these compounds.
The A series share the same rare earth gallosilicate structure, Rb2REGaSi4O12 (RE = Y, Eu, Gd and Tb), constructed by 2-D [GaSi4O12] double layers and 1-D infinite chains formed by edge-sharing REO7. The RE sites on Rb2YGaSi4O12 can be partially substituted by Eu3+ or Tb3+ respectively or simultaneously. These photoluminescent compounds display great potential in the application of phosphor materials.
Different combination of fluxes were used to prepare four new uranyl silicates in B series. B1 and B2 are salt-inclusion structures containing MF (M = alkali ions) octahedraon in their 12-ring channels. B3 is constructed by unusual Si8O2212- oligosilicate anions and discrete Urφ4 tetragonal bipyramids.
In series C, two mixed-valence uranium silicates were synthesized by high temperature, high pressure hydrothermal method with the addition of two alkali cations and fluoride ions. The existence of fluoride ions in synthesis can stabilize the U5+ species (UO2+) and the entry of second alkali metal may induce the mixed-valence uranium in C1 structure. There are three unique uranium sites in C2 and each uranium adopts different valence state. The XPS and XANES data reveal that there are two valences (4+ and 5+) in C1 and three (4+, 5+ and 6+) in C2.

第一章 緒論

1-1 簡介 1-1
1-2 論文研究目標 1-6
1-3 合成方法簡介 1-7
1-3-1 助熔劑長晶法 1-7
1-3-2 水熱法 1-10
1-3-3 藥品一覽表 1-12
1-4 鑑定方法 1-13
1-4-0 儀器測量簡介 1-13
1-4-1 單晶X-ray繞射與結構解析 1-14
1-4-2 粉末X-ray繞射分析 1-16
1-4-3 元素分析 1-17
1-4-4 固態核磁共振分析 1-17
1-4-5 倍頻訊號測量 1-18
1-4-6 紫外-可見光吸收光譜儀 1-19
1-4-7 螢光光譜儀 1-19
1-4-8 X-ray光電子光譜 1-19
1-4-9 X-ray吸收光譜 1-20
1-5 研究成果摘要 1-21
1-6 參考文獻 1-23

第二章 稀土鎵矽酸鹽

2-1 簡介 2-1
2-1-1 稀土元素與稀土矽酸鹽簡介 2-1
2-1-2 發光原理 2-4
2-1-2.1 螢光體簡介 2-4
2-1-2.2 銪與鋱離子發光原理 2-6
2-2 實驗部分 2-11
2-2-1 合成 2-11
2-2-2 單晶X-ray結構解析 2-12
2-3 化合物鑑定 2-13
2-3-1 粉末繞射分析 2-13
2-4 化合物的結構描述與物性測量結果 2-13
2-4-1 Rb2EuGaSi4O12 (A2) 2-13
2-4-1.1 結構描述 2-13
2-4-2 發光性質研究 2-19
2-4-2.1A 化合物A2之光致發光與激發光譜 2-19
2-4-2.1B 化合物A2之放光訊號生命期 2-20
2-4-2.2 化合物A4之光致發光與激發光譜 2-21
2-5 結果與討論 2-22
2-6 參考文獻 2-28

第三章 六價鈾矽酸鹽

3-1 簡介 3-1
3-2 實驗部分 3-5
3-2-1 合成 3-5
3-2-2 單晶X-ray結構解析 3-8
3-3 化合物鑑定 3-10
3-3-1 粉末繞射分析 3-10
3-4 化合物的結構描述與物性測量結果 3-11
3-4-1 [K3Cs4F][(UO2)3(Si2O7)2] (B1) 3-11
3-4-2 [NaRb6F][(UO2)3(Si2O7)2] (B2) 3-16
3-4-3 K6(UO2)3Si8O22 (B3) 3-23
3-4-4 Cs2UO2Si2O6 (B4) 3-28
3-5 結果與討論 3-33
3-5-1 合成討論 3-33
3-5-2 結構比較 3-34
3-6 參考文獻 3-36

第四章 混價鈾矽酸鹽

4-1 簡介 4-1
4-2 實驗部分 4-6
4-2-1 合成 4-6
4-2-2 單晶X-ray結構解析 4-7
4-3 化合物鑑定 4-8
4-3-1 粉末繞射分析 4-8
4-3-2 元素分析 4-9
4-4 化合物的結構描述與物性測量結果 4-9
4-4-1 Cs2K(UO)2Si4O12 4-9
4-4-2 Na7UO2(UO)2(UO2)2Si4O16 4-17
4-5 結果與討論 4-25
4-5-1 合成討論 4-25
4-5-2 結構比較 4-26
4-6 參考文獻 4-29

第五章 總結 5-1

附錄A. A系列晶體數據列表
B系列晶體數據列表
C系列晶體數據列表
附錄B. 化合物粉末X光繞射圖譜
附錄C. 研究所期間發表論文列表

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