臺灣博碩士論文加值系統

本研究是先以化學共沉澱法合成出超順磁奈米氧化鐵並使用具有三個矽烷基與磷苯基的 2-(Diphenylphosphino)ethyltriethoxysilane (DPPES) 將表面修飾官能基後作為載體，再以含浸法將載體上的磷苯基與銠錨定 (anchoring)，分別使用不同溶劑甲醇、甲苯並分別以一鍋法含浸以及分段修飾後再含浸，最後得到超順磁銠鐵複合觸媒 Fe3O4@DPPES-Rh；以 FT-IR、XRD、TEM、EDS、ICP-MS、XPS、SQUID 分析鑑定觸媒，確認奈米氧化鐵粒徑為 10~18 nm，含浸後複合觸媒中銠成分佔 2.50~4.56 wt%，奈米氧化鐵飽和磁化量為 59.39 emu/g，含浸後複合觸媒飽和磁化量為 44.20~33.29 emu/g。
複合觸媒 Fe3O4@DPPES-Rh 應用於氫甲醯化反應 (Hydroformylation)，分別使用不同的溶劑甲苯、乙腈、甲醇，將正己烯作為反應物催化成庚醛，在反應後以外加磁場分離產物與回收觸媒再應用催化反應。產物以氣相層析儀分析選擇性、轉化率與產率並與市售觸媒 RhH(CO)(PPh3)3 比較觸媒的轉化數 (turnover number, TON) 分析複合觸媒催化效果。另外發現在反應中使用甲醇作為溶劑，醛產物會進一步反應成為縮醛。

In this work, we prepared a superparamagnetic iron oxide nanoparticle (SPION) supported phosphine rhodium complex as the catalyst. First, magnetic nanoparticle Fe3O4 prepared via a co-precipitation method was chosen as support. The bare Fe3O4 coated with 2-(diphenphosphino)ethyltriethoxysilane (DPPES) in toluene under reflux to afford the phosphine-functionalized magnetic nanoparticle (Fe3O4@DPPES). The supported rhodium complex (Fe3O4@DPPES-Rh) was obtained by impregnation of RhCl3 with Fe3O4@DPPES in methanol/Toluene through coordination between RhCl3 anchored one the phosphine ligand on Fe3O4 support. The catalyst was characterized by FT-IR, XRD, TEM, EDS, ICP-MS, XPS and SQUID. The TEM image showed that the diameter of Fe3O4 was approximately 10-18 nm. ICP-MS analysis of Fe3O4@DPPES-Rh complexes shows that 0.24-0.44 mmol of Rh was anchored on 1.0 g of NMPs (Rh wt% = 2.5-4.56%). The saturation magnetization of Fe3O4 was 59.39 emu/g and the magnetizations of the Fe3O4@DPPES-Rh were in the range of 44.20-33.29 emu/g.
To evaluate the activity of the catalysts, hydroformylation reactions were chosen as the model reaction. Catalyze the hydroformylation of 1-hexene in different solvents, toluene, acetonitrile, and methanol were used. After the reaction, the catalyst was separated by an external magnetic field and reused. The conversions and the selectivities to products were determined by GC analysis. The turnover number (TON) for aldehyde formation was used to evaluate the activity of the synthesized catalysts and compared to commercially available catalyst, RhH(CO)(PPh3)3. In addition, we found that the aldehyde products could be further converted to acetals when using methanol as solvent.

摘要 I
Abstract II
致謝 IV
目錄 V
圖目錄 IX
表目錄 XII
第一章 緒論 1
1-1 前言 1
1-2 奈米材料 1
1-3 奈米氧化鐵 2
1-4 銠金屬 3
第二章 文獻回顧 4
2-1 奈米氧化鐵合成與修飾 4
2-2 氫甲醯化反應 (Hydroformylation) 11
2-3 實驗動機 12
第三章 實驗部分 13
3-1 實驗藥品 13
3-1.1 反應試劑 13
3-1.2 反應溶劑 14
3-2 儀器分析 14
3-2.1 傅立葉轉換紅外線光譜 (Fourier Transform Infrared Spectroscopy, FTIR) 14
3-2.2 氣相層析-火焰離子化偵測器 (Gas Chromatography-Flame Ionization Detector, GC-FID) 15
3-2.3 氣相層析-質譜儀 (Gas Chromatography-Mass Spectrometry, GC-MS) 16
3-2.4 X-ray粉末繞射儀 (Powder x-ray diffraction, XRD) 16
3-2.5 超導量子干涉磁量儀 (Superconducting Quantum Interference Device Magnetometer, SQUID) 17
3-2.6 穿透式電子顯微鏡（Transmission Electron Microscopy, TEM） 17
3-2.7 能量散射光譜儀（Energy Dispersive Spectrometer, EDS） 18
3-2.8 感應耦合電漿質譜分析儀 (Inductively Coupled Plasma-Mass Spectrometer, ICP-Mass) 18
3-2.9 X- ray 光電子能譜儀 (X-ray Photoelectron Spectrometer, XPS) 19
3-3 實驗步驟 (第一部分 : 觸媒合成) 19
3-3.1 Fe3O4 的合成 19
3-3.2 DPPES 分段修飾 Fe3O4 的合成 (Fe3O4@DPPES) 20
3-3.3 Rh/MeOH含浸 Fe3O4@ DPPES 的合成 (Fe3O4@DPPES-Rh (M) two step) 20
3-3.4 Rh/Toluene含浸 Fe3O4@ DPPES 的合成 (Fe3O4@DPPES-Rh (T) two step) 21
3-3.5 一鍋法含浸 Fe3O4/DPPES/Rh/MeOH (Fe3O4@DPPES-Rh (M) one pot) 21
3-3.6 一鍋法含浸 Fe3O/DPPES/Rh/Toluene (Fe3O4@DPPES-Rh (T) one pot) 22
3-4 實驗步驟 (第二部分 : 催化反應) 23
3-4.1 氫甲醯化反應 (Hydroformylation) 23
3-4.2 觸媒重複氫甲醯化反應 24
3-4.3 建立起始物1-Hexene校正曲線 25
3-4.4 建立產物Heptanal校正曲線 27
3-4.5 氫甲醯化反應產物分析方式 28
第四章 結果與討論 29
4-1 Fe3O4 與 Fe3O4@DPPES 及 Fe3O4@DPPES-Rh 的鑑定與分析 29
4-1.1 Fe3O4 與 Fe3O4@DPPES 的 FT-IR 鑑定 29
4-1.2 Fe3O4 與修飾後觸媒的XRD鑑定 30
4-1.3 Fe3O4 與 Fe3O4@DPPES及 Fe3O4@DPPES-Rh 的 TEM 觀察 31
4-1.4 Fe3O4@DPPES-Rh 的 ICP-MS 分析 34
4-1.5 Fe3O4@DPPES-Rh 的 XPS 分析 35
4-1.6 Fe3O4 與 Fe3O4@DPPES-Rh 的 SQUID 磁性分析 36
4-2 氫甲醯化反應產物分析 37
4-2.1 GC-FID的分析 37
4-2.2 氫甲醯化-縮醛化反應 (Hydroformylation–Acetalization) 61
結論 66
參考文獻 68

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