含三價稀土元素配位聚合物內能量轉移之研究｜國立中央大學博碩士論文系統

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研究生：	李穗美 Sui-mei Lee
論文名稱：	含三價稀土元素配位聚合物內能量轉移之研究
指導教授：	張伯琛 Bor-chen Chang
口試委員:
學位類別：	碩士 Master
系所名稱：	理學院 - 化學學系 Department of Chemistry
論文出版年：	2015
畢業學年度：	103
語文別：	中文
論文頁數：	105
中文關鍵詞：	稀土元素、能量轉移
相關次數：	點閱：17 下載：0
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本論文利用中溫水熱法合成以1,4-cyclohexanedicarboxylate (C8H10O4, 簡稱CHDC)作為配位基含有不同莫耳比例稀土元素之R2(CHDC)3配位聚合物晶體(R= Y, Eu, Tb, Sm)。這些化合物皆以單晶及粉末X光繞射圖譜確認晶體之結構與純度，並以感應耦合電漿原子發射光譜分析儀(ICP-AES)鑑定配位中心的元素比例。YxEuyTb2-x-y(CHDC)3化合物之光致放光光譜、激發光譜及其時間解析光譜在實驗中取得後，我們提出了一個動力學模型成功地解釋在YxEuyTb2-x-y(CHDC)3化合物中之能量轉移現象並求出相關速率常數。此外，以性質相近之Sm3+取代Eu3+合成一系列之YxSmyTb2-x-y(CHDC)3化合物並測
量這些化合物的光譜資料，並套用於我們所提出的動力學模型來分析，我們證明此動力學模型能完整詮釋CHDC配位聚合物中之能量轉移現象。

Mid-temperature hydrothermal technique has been adopted for the synthesis of a series of coordination polymers, R2(C8H10O4)3, (R= Y, Eu, Tb, and Sm; C8H10O4= 1,4-cyclohexanedicarboxylate, CHDC) with different compositions.
Single-crystal and powder X-ray diffraction (XRD) data of these compounds were obtained for confirming their structure and purity. The photoluminescence spectra, excitation spectra, and time-resolved spectra of YxEuyTb2-x-y(CHDC)3 compounds were recorded. We proposed a kinetics model which successfully explains the energy transfer processes between luminescent centers and related rate constants. Additionally, when Eu3+ is replaced by Sm3+, a series of YxSmyTb2-x-y(CHDC)3 compounds were synthesized. Their related spectroscopic
data were also acquired and analyzed by our model. We have shown that the proposed kinetics model can successfully describe the energy transfer processes
in the CHDC coordination polymers.

中文摘要 ................................................................................................................ I
英文摘要 .............................................................................................................. II
謝誌 ..................................................................................................................... III
圖目錄 ................................................................................................................ VII
表目錄 .................................................................................................................. X
第一章 緒論 ......................................................................................................... 1
1-1 鑭系元素與稀土元素 ........................................................................... 1
1-2 鑭系元素之發光原理 ........................................................................... 4
1-2-1 銪離子之發光 ............................................................................. 5
1-2-2 鋱離子發光原理 ......................................................................... 8
1-2-3 釤離子發光原理 ......................................................................... 8
1-3 先前研究 ................................................................................................. 9
1-4 論文研究目標....................................................................................... 13
第二章 實驗 ....................................................................................................... 15
2-1 實驗目標 .............................................................................................. 15
V
2-2 合成方法簡介...................................................................................... 15
2-2-1 中溫水熱合成法 ...................................................................... 16
2-2-2 R2(CHDC)3 晶體製備 ............................................................... 18
2-2-3 使用藥品 .................................................................................. 19
2-3 鑑定方法 .............................................................................................. 19
2-3-1 單晶 X 光繞射實驗與晶體結構解析 .................................... 19
2-3-2 粉末 X 光繞射分析 ............................................................... 22
2-3-3 感應耦合電漿原子發射光譜儀 .............................................. 22
2-4 光譜實驗簡介...................................................................................... 23
2-5 光譜量測元件簡介 ............................................................................. 25
2-5-1 光源 .......................................................................................... 25
2-5-2 單光儀 ...................................................................................... 26
2-5-3 偵測器 ...................................................................................... 27
2-5-4 示波器 ...................................................................................... 29
2-6 光譜分析研究及儀器裝置 .................................................................. 29
2-6-1 光致放光光譜 ........................................................................... 29
2-6-2 激發光譜 ................................................................................... 31
2-6-3 時間解析光譜 ........................................................................... 33
第三章 結果與討論 ........................................................................................... 35
VI
3-1 YxEuyTb2-x-y(CHDC)3 ........................................................................... 35
3-1-1 晶體鑑定 .................................................................................. 35
3-1-2 晶體結構 .................................................................................. 38
3-1-3 光致放光光譜 .......................................................................... 40
3-1-4 激發光譜 .................................................................................. 41
3-1-5 Tb3+之放光衰退曲線 ................................................................ 45
3-1-6 Eu 3+訊號上升曲線之量測與模擬 ........................................... 51
3-2 YxSmyTb2-x-y(CHDC)3 ........................................................................... 62
3-2-1 晶體鑑定 ................................................................................... 62
3-2-2 光致放光光譜 .......................................................................... 63
3-2-3 激發光譜 .................................................................................. 66
3-2-4 以303.5 nm 雷射激發之Tb3+放光衰退曲線......................... 67
3-2-5 以303.5nm 雷射激發之Sm3+光譜資訊 ................................. 69
3-2-6 以546 nm 雷射激發之放光光譜 ............................................ 70
3-2-7 以546 nm 雷射激發之Tb3+與Sm3+放光衰退曲線 .............. 72
3-2-8 以546 nm 雷射激發之Sm3+訊號上升曲線與模擬 ............... 76
第四章 結論 ....................................................................................................... 86
參考文獻 ............................................................................................................. 89
附錄 ..................................................................................................................... 91
                                

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