臺灣博碩士論文加值系統

本篇論文參考王建舜學長的研究成功地合成出具含氮雜環碳烯 (NHC) 之間距分子 (Mesbim)(CH2)11SH (8)，並以錨定硫醇之金奈米粒子[Au-SR] (R = CH3(CH2)6CH2SH) (9) 作為載體，加入間距分子 (Mesbim)(CH2)11SH (8) 與金奈米粒子表面的硫醇保護基作交換 (place exchange)，得到 RS-Au-Smes (10)。另外合成出具 NHC 之分子觸媒 [HOOCMMIM][PF6] (2)，並以氧化鋅奈米粒子作為載體，加入分子觸媒 [HOOCMMIM][PF6] (2)，得到氧化鋅載體式觸媒 ZnO-[HOOCMMIM][PF6] (3)。由於將有機分子修飾在奈米粒子上時，能使載體式觸媒溶解 (或分散) 於有機溶劑中，因此可利用液相核磁共振光譜儀 (NMR) 快速準確地觀察其結構，另外也利用穿透式電子顯微鏡 (TEM) 鑑定奈米粒子之粒徑大小。
含氮雜環碳烯常用於形成醛基之間的 C-C 鍵，因此我們將 NHC離子液體觸媒及氧化鋅奈米粒子觸媒應用於羥醛縮合反應。也因為此類催化劑能將醛類進行親核化，所以也嘗試催化親核取代反應。結果分子式觸媒 [HOOCMMIM][PF6] (2) 及氧化鋅奈米粒子觸媒ZnO-[HOOCMMIM][PF6] (3) 進行的催化效果極其相似，說明作為載體的氧化鋅並不會影響錨定在表面的分子觸媒之活性。
最後，我們以氧化鋅奈米粒子能夠以簡單的方式從反應系統中分離的特性，測試其重複催化的能力。實驗結果顯示奈米粒子載體催化劑能夠進行 12 次的重複催化實驗，且第 12 次實驗之催化產率能在 85 % 以上，說明利用奈米粒子載體分子式觸媒能夠節省製造催化劑之成本、減少在反應後進行分離作業的時間及減少不必要的浪費。

We refered to Wang’s thesis, sythesized the N-heterocyclic carbenes (NHCs) molecules, (Mesbim)(CH2)11SH (8), used gold nanoparticles anchored thiol protecting groups [Au-SR] (R = CH3(CH2)6CH2SH) (9) as the carrier, and exchanged part of protecting groups to (Mesbim)(CH2)11SH (8), finally we got gold nanoparticles supported catalyst RS-Au-Smes (10). The other side, we sythesized another NHCs molecular catalyst, [HOOCMMIM][PF6] (2), and anchored on ZnO nanoparticles to make the zinc oxide nanoparticles supported catalysts ZnO-[HOOCMMIM][PF6] (3). According to theese nanoparticles supported organic molecules could be well dispersed in organic solvents, we did the quick and accurate structure identification by solution NMR and TEM.
NHCs were usually applicated on forming C-C bond between aldehydes, therefore, we utilized the NHCs molecular catalyst, [HOOCMMIM][PF6] (2), on aldol condensation reaction. In addition, the NHCs ion liquid could make aldehydes nucleophilic during the condensation catalysus, so we also attempted to catalize nucliphilic substution reaction, these catalytic consequents of two reactions were compared with zinc oxide nanoparticles supported catalysts ZnO-[HOOCMMIM][PF6] (3). We discover the catalytic consequents were very close, this result illstrated that the ZnO nanopaticles as carrier would not reduce catalytic activity of organic catalysts.
Finally, we did the recycling and re-catalization test of ZnO-[HOOCMMIM][PF6] (3), we found the nanoparticle catalysts could make 85 % catalysis yield after 12 recycles. That was to say, the nanoparticle-supported molecular catalysts would cut the cost of producing the molecule, by the way, it could decrease the recycling time and the unnecessary wastes.

中文摘要 I
Abstract III
總目錄 V
表目錄 VIII
圖目錄 X
附圖目錄 XII
一、緒論 1
1.1 混成相載體式觸媒 1
1.2 混成相觸媒的組成 3
1.3 混成相觸媒載體分類 5
1.3.1 有機高分子 (organic polymers) 載體 5
1.3.2 矽膠高分子 (silica gel) 載體 7
1.3.3 無機金屬氧化物 (metal oxides) 載體 9
1.3.4 金奈米粒子 (gold nanoparticles) 載體 12
1.4 氧化鋅奈米粒子 16
1.4.1 鋅金屬 16
1.4.2 氧化鋅奈米粒子的催化活性 17
1.4.3 氧化鋅奈米粒子之穩定性及其工業應用價值 20
1.5 含氮雜環碳烯 (N-Heterocyclic Carbenes, NHCs) 22
1.5.1 含氮雜環碳烯的發現 22
1.5.2 含氮雜環碳烯的合成 23
1.5.3 含氮雜環碳烯的催化應用 25
1.6 親核取代 (Nucleophilic Substitution) 反應之介紹 29
1.7 羥醛縮合 (Aldol Condensation) 反應之介紹 35
1.7.1 羥醛縮合反應之催化機制 35
1.7.2 羥醛縮合反應之發展 36
1.8 研究動機 41
二、實驗部分 42
2.1 氧化鋅奈米粒子觸媒製備 44
2.1.1 化合物 [HOOCMMIM][Br] (1) 的製備 44
2.1.2 離子液體 [HOOCMMIM][PF6] (2) 製備 45
2.1.3 氧化鋅奈米粒子載體分子式觸媒 ZnO-[HOOCMMIM][PF6] (3) 製備 46
2.2 金奈米粒子載體式觸媒製備 47
2.2.1 化合物 1-mesityl-1H-imidazole (4) 的製備 47
2.2.2 11-bromoundec-1-ene (5) 製備 48
2.2.3 11-bromoundecyl ethanethioate (6) 的製備 49
2.2.4 11-bromoundecane-1-thiol (7) 的製備 50
2.2.5 間距分子 (Mesbim)(CH2)11SH (8) 的製備 50
2.2.6 金奈米粒子載體 [Au-SR (R = C8H17)] (9) 製備 51
2.2.7 RS-Au-SMes (10) 製備 53
2.3 氧化鋅奈米粒子觸媒在親核取代反應之應用 54
2.3.1 產物光譜數據 54
2.4 氧化鋅奈米粒子在羥醛縮合反應之應用 57
2.4.1 產物光譜數據 57
2.5 載體式觸媒的回收再利用 60
三、結果與討論 61
3.1載體式分子觸媒 ZnO-[HOOCMMIM][PF6] (3) 和 RS-Au-SMes (10) 的合成策略 62
3.1.1 ZnO-[HOOCMMIM][PF6] (3) 的合成探討 62
3.1.2 載體式分子觸媒 RS-Au-SMes (10) 的合成探討 63
3.2載體式觸媒 ZnO-[HOOCMMIM][PF6] (3) 結構鑑定 64
3.2.1核磁共振光譜儀 (1H-NMR) 之結構鑑定 64
3.2.2 TEM 影像及 EDS 鑑定 65
3.3 載體式觸媒 RS-Au-SMes (10) 結構鑑定 66
3.3.1 核磁共振光譜儀 (1H-NMR) 之結構鑑定 66
3.3.2 TEM 影像及 EDS 鑑定 67
3.4 載體式觸媒定量分析及 NMR 定量法 68
3.4.1 載體式觸媒 ZnO-[HOOCMMIM][PF6] (3) 定量分析 68
3.5 氧化鋅奈米粒子觸媒對親核取代反應之應用 71
3.5.1 分子式觸媒 [HOOCMMIM][PF6] (2) 催化親核取代反應條件探討 71
3.5.2 分子式觸媒 [HOOCMMIM][PF6] (2) 對多種苯甲基類分子於親核取代反應之應用 73
3.5.3 氧化鋅奈米粒子載體式觸媒對分子式觸媒之催化效果比較 79
3.5.4 氧化鋅奈米粒子對親核取代反應之重複利用 81
3.5.5 親核取代反應之催化機制 84
3.6 分子式觸媒 [HOOCMMIM][PF6] (2) 對羥醛縮合反應的探討 86
3.6.1 羥醛縮合反應催化條件探討 86
3.6.2 以氧化鋅奈米粒子觸媒 ZnO-[HOOCMMIM][PF6] (3) 對多種醛類進行羥醛縮合反應 88
3.6.3 羥醛縮合反應之催化機制 90
四、結論 91
五、參考文獻 92

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