臺灣博碩士論文加值系統

本研究收集分屬沸石二級架構單元的沸石標本，進行拉曼光譜的分析，以求得區分不同架構單元的特徵峰，作為未來建立沸石拉曼光譜資料庫的參考依據。再以熱重分析並配合X光粉末繞射與拉曼光譜分析，探討沸石之熱穩定性。因此，針對各類沸石進行結構及熱穩定性分析，並配合電子微探分析以確定化學成分，對沸石拉曼振動模進行初步比對與探討頻譜之變化，並進一步找出拉曼光譜與化學成分之關連性。分析結果顯示，相同二級架構單元連結方式之沸石，具有相似之拉曼光譜，但是會隨著化學成分之不同，而有所差異。主要的拉曼峰值幾乎皆出現在390~530 cm-1，為T-O-T ( T = Si, Al ) 鍵結中氧原子運動之振動所造成的，分析此波數範圍，找出彼此相近的拉曼特徵峰，以此原則即可區分不同構造單元之沸石。
實驗結果顯示，可用於區別二級架構單元的拉曼特徵峰分別為：纖維狀沸石出現在436~445 cm-1與533~537 cm-1；單連結四環鏈沸石出現在380~389 cm-1；雙連結四環鏈沸石出現在421~426 cm-1。六環沸石出現在477~484cm-1。片沸石群出現404~410 cm-1。
雙連結四環鏈沸石，會隨著Al的含量增加，使T-O-T鍵結中氧原子運動之振動頻率有降低之趨勢。但在六環沸石中，隨著Al含量的增加，對T-O-T鍵結之振動頻率並未有顯著之影響。在片沸石群中，Al含量的變化對T-O-T的振動頻率之影響並不顯著。
熱穩定性方面，Chabazite、Mordenite、Analcime以及Merlinoite升溫至600℃，由X光粉末繞射分析結果顯示，結構並未明顯破壞，確認此類型之沸石熱穩定性高 (類型1)。Clinoptilolite、Scolecite、Laumontite以及Na-phillipsite升溫至400℃以上，結構會略有破壞並產生礦物相的變化，確認此類型沸石的熱穩定性較前者差 (類型2 )。Heulandite升溫至400℃以上，結構已完全破壞，且完全轉變為非晶質，確認此類型沸石的熱穩定性低 (類型3)。

This study collected zeolite specimens of different secondary building units. Each sample was investigated by Raman Spectrum analyses to get their specific peaks of different building units, and to establish the Raman spectrum database in the future. Zeolite specimens were examined by thermogravimetric analysis. X-ray diffraction and Raman spectroscopy analyses are used to study thermal stability of zeolite. So this study investigates structure and thermal stability in different kind of zeolites. We
investigate by electron probe microanalysis of the identification of chemical composition. Raman vibration modes of zeolite are assign and investigating variation of frequency. We try to investigate the relation
between Raman spectroscopy and chemical composition. The result inhibits the same secondary building units of zeolite have similar Raman Spectrum. Major Raman peaks all appear in the range of 390~530cm-1, which are assigned the oxygen atom vibration in T-O-T bond (T= Si, Al). We analyzed the range of wavenumber and found the nearly Raman characteritic peaks, and we can differentiate the different building units of zeolites based on this method.
The experimental results show the Raman specific peaks of different secondary building are classified as follows: fibrous zeolites appear in the ranges of 436~445 cm-1 and 533~537 cm-1 ; single connected 4-ring chains zeolites appear in the range of 380~389 cm-1 ; doubly 4-ring chains zeolites appear in the range of 421~426 cm-1 ; 6-ring zeolites appear in the range of 477~484 cm-1; heulandite group appear in the range of 404~410 cm-1.
As Al contents increase in the single connected 4-ring chains zeolites；
It leads to decrease frequency of oxygen atom vibrationa in T-O-T bond . But Al contents increase in the 6-rings zeolites, with little change frequency
of oxygen atom vibrationa of in T-O-T bond. As Al contents increase in the heulandite group , vibrational frequency in the T-O-T bond have any changes .
In thermal stability aspect, Chabazite、Mordenite、Analcime and
Merlinoite heat temperatures at 600℃，The experimental results show from X-ray powder diffraction study, Structure has little breakdown significantly. We consider the type of zeolite which thermal stability is very stable (category 1). Clinoptilolite、Scolecite、Laumontite and Na-phillipsite heat temperatures at 600℃. It occurs structural breakdown slightly and induced to phase transformation of minerals. We consider the kind of zeolite in thermal stability bad than category 1. Heulandite heats temperatures up 400℃. The experimental result occurs structural breakdown completely, to transform amorphous. Thermal stability in the type zeolite is unstable (category 3).
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目錄
摘要………………………………………………………………………Ⅰ
Abstract………………………………………………………………Ⅲ
目錄………………………………………………………………………Ⅴ
表目………………………………………………………………………Ⅷ

圖目……………………………………………………………………....Ⅹ


第一章 緒論…………………………………………………………….1
1.1 前言……………………………………………………………1
1.2 沸石的定義和分類……………………………………………4
1.3 拉曼光譜的原理………………………………………………12
1.4 前人研究………………………………………………………15
1.5 研究目的………………………………………………………17
第二章 實驗方法與步驟……………………………………………….18
2.1 實驗材料………………………………………………………18
2.2 實驗儀器………………………………………………………23
2.3 實驗方法………………………………………………………25
2.3.1 合成沸石……………………………………………….27
2.3.2 拉曼光譜分析………………………………………….28
2.3.3 掃描式電子顯微鏡分析……………………………….28
2.3.4 X光粉末繞射分析…………………………………….29
2.3.5 電子微探儀分析……………………………………….29
2.3.6 熱重分析……………………………………………….30
第三章 實驗結果……………………………………………………….32
3.1 沸石之拉曼光譜………………………………………………32
3.1.1 纖維狀沸石…………………………………………….33
3.1.2 單連結四環鏈沸石…………………………………….33
3.1.3 雙連結四環鏈沸石…………………………………….34
3.1.4 六環沸石……………………………………………….34
3.1.5 絲光沸石群…………………………………………….35
3.1.6 片沸石群…….…………………………………………35
3.2 沸石的化學成分………………………………………………56
3.3 熱重分析結果…………………………………………………68
第四章 討論…………………………………………………………...84
4.1 沸石之拉曼特徵峰……………………………………………84
4.2 化學成分對沸石的拉曼振動模之影響………………………88
4.2.1 雙連結四環鏈沸石…………………………………...88
4.2.2 六環沸石…………………………………………….100
4.2.3 片沸石群…………………………………………….105
4.3 溫度對沸石的礦物相與結構之影響………………………..115
第五章 結論…………………………………………………………...118
參考文獻……………………………………………………………….119
附錄A 沸石標本照片……………………………………………….124
附錄B X光粉末繞射圖 …………………………………………...131
附錄C 沸石的化學成分…………………………………………….142
附錄D 沸石的熱重分析圖………………………………………….154

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