臺灣博碩士論文加值系統

本研究嘗試以兩階段合成方式生成具有高比表面積的金屬氧化物奈米薄片。在第一階段時，分別將鄰苯二胺、正十六胺和三聚氰胺三種有機分子插層至HNbWO6 • 1.5H2O和HTaWO6 • 1.5H2O水合層狀金屬氧化物。在第二階段時，則是選擇甲苯，二氯甲烷和四氫呋喃三種不同極性的有機溶劑並利用超音波震盪，將有機-無機層狀金屬氧化合物的層狀物剝層，以得到奈米化的層狀薄片。最後，將所得到奈米薄片作為乙酸酯化反應之固體酸催化劑使用，並透過氣相層析進一步評估催化效果。

The present study is an attempt to generate a new way for the synthesis of two dimensional nanosheets which has a higher specific surface area and better catalytic properties. The synthesis was carried out in two steps, intercalation of the layered materials with organic entities followed by exfoliation in various nonpolar solvents. The layered oxide materials HNbWO6 • 1.5H2O and HTaWO6 • 1.5H2O were utilized as the precursors for the synthesis of nanosheets. The organic compounds- ortho-phenylenediamine, hexadecylamine and melamine were intercalated into the host materials at room temperature. Further ultra-sonication was carried out in nonpolar solvents- toluene, dichloromethane and tetrahydrofuran correspondingly. The obtained solid acid nanosheets were applied in the acetic acid esterification reaction as catalyst and the performance was further evaluated through gas chromatography.

目次
目次 III
圖次 V
表次 VIII
第一章 緒論 1
1.1研究動機 1
1.2層狀金屬氧化物結構 2
1.3水合層狀金屬氧化物（HNW / HTW）酸鹼度 6
1.4催化反應（catalytic reactions） 7
1.4.1酯化反應的催化 8
1.5有機-無機複合材料奈米化 10
1.5.1插層有機客體分子的選擇 11
1.5.2奈米剝層溶劑選擇（nano-exfoliation） 14
第二章 藥品與儀器 15
2.1藥品 15
2.2儀器 16
2.2.1粉末X光繞射儀（Powder X-ray Diffractometer, XRD） 16
2.2.2熱重分析儀（Thermogravimetric Analyzer, TGA） 16
2.2.3掃描式電子顯微鏡（Scanning Electron Microscope, SEM） 17
2.2.4能量分散光譜儀（Energy Dispersive X-ray Spectroscopy, EDS） 17
2.2.5基質輔助雷射脫附離子化－飛行時間質譜儀（Matrix Assisted Laser Desorption / Ionization-Time of Flight Mass Spectrometer，MALDI-TOF MS） 18
2.2.6傅立葉轉換紅外線光譜儀（Fourier Transform Infrared Spectroscopy，FTIR） 19
2.2.7動態光散射（Dynamic Light Scatteringy，DLS） 19
2.2.8氣相層析儀（Gas Chromatography，GC） 20
第三章 實驗流程 22
3.1 合成無機層狀化合物 23
3.1.1 合成LiMWO6 （M = Nb or Ta） 23
3.1.2 合成HNW / HTW 23
3.2 有機客體分子插層至無機層狀化合物 24
3.2.1 oPDA插層至HNW / HTW 24
3.2.2 C16插層至HNW / HTW 24
3.2.3 Mel插層至HNW / HTW 25
3.3 有機-無機複合材料奈米化 26
3.4 有機-無機複合材料料催化酯化反應 26
第四章 結果與討論 27
4.1有機-無機複合材料合成 27
4.1.1水合金屬層狀物 27
4.1.2有機客體插層反應 29
4.2有機-無機複合材料剝層反應（exfoliation） 47
4.3催化酯化反應實驗 55
4.3.1 乙酸乙酯定量 56
第五章 結論 60
第六章 參考文獻 61
第七章 附錄 65
附錄一 65
附錄二 67


圖次
圖1. 層狀氧化合物示意圖19 4
圖2. Fridel-Crafts alkylation示意圖 9
圖3. 酯化反應（esterification）反應機制28 9
圖4. 有機-無機複合材料奈米化示意圖29 10
圖5.（a）苯二胺同分異構物示意圖（b）正十六胺（c）三聚氰胺 13
圖6. 奈米化樣品與溶劑關係示意圖 14
圖7. GC 示意圖 20
圖8. LiNbWO6 / LiTaWO6高溫燒解 23
圖9. 合成HNW / HTW之步驟 23
圖10. PDA生成有機-無機復合材之步驟 24
圖11. C16生成有機-無機復合材之步驟 25
圖12. Mel生成有機-無機復合材之步驟 25
圖13. 奈米化流程 26
圖14. 乙酸酯化反應流程 26
圖15. （a）LiNbWO6（b）LiTaWO6（c）HNW（d）HTW 28
圖16. （a）HNW（b）oPDA-HNWa（c）C16-HNWa（d）Mel-HNWa複合材料之粉末繞射圖 31
圖17. （a）HTW（b）oPDA-HTWa（c）C16-HTWa（d）Mel-HTWa 複合材料之粉末繞射圖 31
圖18. （a）HNW（b）oPDA-HNWa（c）C16-HNWa（d）Mel-HNWa複合材料之FT-IR光譜圖 33
圖19. （a）HTW（b）oPDA-HTWa（c）C16-HTWa（d）Mel-HTWa複合材料之 FT-IR光譜圖 34
圖20. oPDA聚合反應機 36
圖21. （a）DHB基質（b）oPDA-HNWa 37
（c）C16-HNWa（d）MeL-HNWa 之MALDI-TOF-MS圖（以*表示基質） 37
圖22. （a）DHB基質（b）oPDA-HTWa 37
（c）C16-HTWa（d）MeL-HTW之 MALDI-TOF-MS圖（以*表示基質） 37
圖23. oPDA-HNWa / HTWa 以及 C16- HNWa / HTWa 以及 Mel- HNWa / HTWa有機-無機複合材料之TGA圖 40
圖24. oPDA插層層狀物可能排列方式示意圖 41
圖25. Mel插層層狀物可能排列方式示意圖31 42
圖26. C16插層層狀物可能排列方式示意圖 43
圖27. oPDA- HNWa /HTWa複合材料經JADE 5 軟體理論精算(藍實線)與實際繞射(黑實線)比對及密勒指數面 44
圖28. C16- HNWa /HTWa複合材料經JADE 5 軟體理論精算(藍實線)與實際繞射(黑實線)比對及密勒指數面 45
圖29. Mel- HNWa /HTWa複合材料經JADE 5 軟體理論精算(藍實線)與實際繞射(黑實線)比對及密勒指數面 46
圖30. （a）oPDA-HNWa（b）C16-HNWa（c）Mel-HNWa在toluene溶劑中的粒徑分佈 48
圖31. （a）oPDA-HNWa（b）C16-HNWa（c）Mel-HNWa 在DCM 溶劑中的粒徑分佈 49
圖32. （a）oPDA-HNWa（b）C16-HNWa （c）HNW在THF溶劑中的粒徑分佈 50
圖33. 以365 nm UV燈照射（a）THF（b）HNW（c）oPDA-HNWa（d）C16-HNWa（e）Mel-HNWa所產生的螢光影像 51
圖34. 以365 nm UV燈照射（a）THF（b）HTW（c）oPDA-HTWa（d）C16-HTWa（e）Mel-HTWa所產生的螢光影像 51
圖35. THF溶劑之NMR圖 52
圖36. HNW水合層狀物分散在THF溶劑之NMR圖 53
圖37. HTW水合層狀物分散在THF溶劑之NMR圖 54
圖38. 乙酸乙酯檢量線 55
圖39. HNW催化乙酸酯化反應GC量測圖 56


表次
表1. LiMWO6及HNW / HTW 2結構參數 5
表2. 有機物酸度係數（pKa） 12
表3. 胺類鹼性度大小之比較 29
表4. FT-IR 三種有機客體分子官能基 32
表5. 複合材料經JADE 5軟體理論精算結果 43
表6. 未奈米化HNW / HTW催化乙酸乙酯之GC定量 56
表7. 0.005 g有機-無機複合材料催化乙酸乙酯之GC定量 59

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