臺灣博碩士論文加值系統

本研究主要將奈米金粒子及還原氧化石墨烯添加到電活性聚醯胺(Electroactive Polyamide, EPA)當中，形成電活性聚醯胺複合材料並作為催化劑應用於催化還原對-硝基苯酚，其主要分為三部分。
第一部分是利用氧化偶合法合成電活性聚醯胺並利用傅立葉紅外線光譜儀(FTIR)、質譜儀(LC-MS)、核磁共振儀(NMR)及凝膠滲透層析儀(GPC)對其官能基、結構及分子量進行鑑定。利用紫外光-可見光光譜儀(UV-vis)及循環伏安儀(CV)量測其化學氧化還原及電活性之特性。
第二部分為利用電活性聚醯胺作為奈米金粒子之載體及還原劑，合成系列金/電活性聚醯胺(Au/EPA)複合材料，作為催化還原對-硝基苯酚之催化劑。並由FTIR鑑定其官能基，X光繞射分析儀(XRD)及X射線光電子能譜儀(XPS)鑑定奈米金粒子的結構，CV鑑定其電活性，場發射電子顯微鏡(SEM)及穿透式電子顯微鏡(TEM)對金/電活性聚醯胺複合材料之形貌作鑑定。由研究結果可知金/電活性聚醯胺複合材料具有良好的催化還原對-硝基苯酚之特性，其催化還原對-硝基苯酚之反應速率常數分別為6.1×10-3 s-1 (1 Au/EPA)、7.4×10-3 s-1 (3 Au/EPA)及 7.6×10-3 s-1 (5 Au/EPA)。再由催化還原對-硝基苯酚效果最佳的5 Au/EPA複合材料進行溫度對催化還原對-硝基苯酚的影響，計算出催化還原對-硝基苯酚的活化能為28.10 kJ/mol。
第三部分則是先將氧化石墨烯(GO)及還原氧化石墨烯(RGO)添加到電活性聚醯胺當中，藉由提高電活性聚醯胺的氧化還原特性，進一步探討其還原奈米金粒子之能力，製備出金/氧化石墨烯/電活性聚醯胺(Au/GO/EPA)及金/還原氧化石墨烯/電活性聚醯胺(Au/RGO/EPA)複合材料並探討其對催化還原對-硝基苯酚之效果。由CV可知GO/EPA及RGO/EPA複合材料的氧化還原能力皆有提高，進一步利用GO/EPA及RGO/EPA作為還原奈米金粒子之載體及還原劑，合成Au/GO/EPA及Au/RGO/EPA複合材料，作為催化還原對-硝基苯酚之催化劑。由XRD及XPS鑑定結果可知奈米金粒子已成功製備，且Au/GO/EPA及Au/RGO/EPA複合材料作為催化劑還原對-硝基苯酚的效果有進一步提升，其反應速率常數分別為1.05×10-2 s-1及1.15×10-2 s-1；活化能分別為38.99 kJ/mol及37.29 kJ/mol。

In this dissertation, Au nanoparticles and graphene were introduced in electroactive polyamide (EPA) to prepare the EPA composites catalyst for 4-nitrophenol reduction. This dissertation is mainly divided into three parts.
In the first part, the EPA was synthesized by an oxidative coupling reaction, and it was characterized by Fourier-transform infrared (FTIR), Liquid chromatography-mass spectrometry (LC-MS), Nuclear Magnetic Resonance spectrometry (NMR), and gel permeation chromatography (GPC). The reversible redox activity of the EPA was monitored by UV–vis spectroscopy (UV-vis). Moreover, the electroactivity of the EPA was evaluated by electrochemical cyclic voltammetry (CV).
In the second part, the as-prepared EPA was used as a carrier and reducing agent for Au nanoparticles to synthesize a series of Au/EPA composite catalysts for the reduction of 4-nitrophenol. The synthesized Au/EPA composites were characterized by FTIR, CV, X-ray diffractometer (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and UV-vis. The prepared 1 Au/EPA, 3 Au/EPA, and 5 Au/EPA were found to exhibit catalytic activity towards 4-nitrophenol with a rate constant of 6.1×10-3 s-1, 7.4×10-3 s-1, and 7.6×10-3 s-1, respectively. The activation energy (Ea) for 5 Au/EPA is 28.10 kJ/mol.
In the third part, the GO/EPA and RGO/EPA composites were prepared by incorporated graphene oxide (GO) and graphene (RGO) into EPA to improve the redox activity. Furthermore, the as-prepared GO/EPA and RGO/EPA were used as a carrier and reducing agent for reducing Au nanoparticles to synthesize Au/GO/EPA and Au/RGO/EPA composite catalysts for the reduction of 4-nitrophenol. The synthesized Au/GO/EPA and Au/RGO/EPA composites were characterized by FTIR, CV, XRD, XPS, SEM, TEM, and UV-vis. The prepared Au/GO/EPA and Au/RGO/EPA were found to exhibit catalytic activity towards 4-nitrophenol with a rate constant of 1.05×10-2 s-1 and 1.15×10-2 s-1, respectively. The activation energy for Au/GO/EPA and Au/RGO/EPA is 38.99 kJ/mol and 37.29 kJ/mol, respectively.

中文摘要 I
ABSTRACT III
致謝 V
目錄 VI
圖目錄 X
表目錄 XVII
第一章 導論 1
1.1 前言 1
1.2 芳香族化合物 2
1.2.1 酚類化合物 4
1.2.2 處理水溶性芳香族化合物之方法 5
1.3 奈米金屬粒子簡介 7
1.3.1 局部表面電漿共振 8
1.4 催化劑材料用於催化硝基苯酚化合物之文獻回顧 9
1.5 研究動機 22
第二章 電活性聚醯胺之合成與鑑定 24
2.1 導電高分子材料的種類 24
2.1.1 本質型導電高分子之簡介 25
2.1.2 聚苯胺之簡介 26
2.2 電活性高分子之簡介 27
2.3 電活性高分子及其複合材料之文獻回顧 27
2.4 研究動機 31
2.5 實驗 32
2.5.1 實驗藥品 32
2.5.2 儀器設備及分析條件 34
2.6 電活性聚醯胺之合成 36
2.6.1 醯胺寡聚物之合成 36
2.6.2 電活性聚醯胺之合成 37
2.7 鑑定 38
2.7.1 醯胺寡聚物之鑑定 38
2.7.2 電活性聚醯胺之鑑定 41
2.7.3 電活性聚醯胺之化學氧化分析 43
2.7.4 電活性聚醯胺之電活性測試 44
2.7.5 電活性聚醯胺之形貌鑑定 45
2.8 結論 46
第三章 金/電活性聚醯胺複合材料之合成、鑑定及將其應用在催化還原對硝基苯酚之探討 47
3.1 奈米金屬粒子/高分子複合材料用於催化還原對-硝基苯酚之文獻回顧 47
3.2 研究動機 54
3.3 實驗 55
3.3.1 實驗藥品 55
3.3.2 儀器設備及分析條件 55
3.3.3 金/電活性聚醯胺複合材料之合成 57
3.3.4 代號說明 57
3.3.5 催化還原對-硝基苯酚 58
3.4 結果與討論 59
3.4.1 金/電活性聚醯胺複合材料之FTIR鑑定 59
3.4.2 金/電活性聚醯胺複合材料之CV鑑定 62
3.4.3 金/電活性聚醯胺複合材料之XRD鑑定 63
3.4.4 金/電活性聚醯胺複合材料之XPS鑑定 64
3.4.5 金/電活性聚醯胺複合材料之TGA鑑定 66
3.4.6 金/電活性聚醯胺複合材料之形貌鑑定 67
3.4.7 金/電活性聚醯胺複合材料用於催化還原對-硝基苯酚之探討 72
3.5 結論 78
第四章 金/還原氧化石墨烯/電活性聚醯胺複合材料及金/氧化石墨烯/電活性聚醯胺複合材料之合成、鑑定及將其應用在催化還原對硝基苯酚之探討 79
4.1 石墨烯及氧化石墨烯之簡介 79
4.1.1 石墨烯簡介 79
4.1.2 氧化石墨烯簡介 80
4.1.3 氧化石墨烯之製備方法 80
4.2 石墨烯及氧化石墨烯/高分子複合材料之文獻回顧 84
4.3 研究動機 86
4.4 實驗 87
4.4.1 實驗藥品 87
4.4.2 儀器設備及分析條件 87
4.4.3 氧化石墨烯及還原氧化石墨烯之合成 88
4.4.4 氧化石墨烯/電活性聚醯胺、還原氧化石墨烯/電活性聚醯胺複合材料之合成 89
4.4.5 金/氧化石墨烯/電活性聚醯胺及金/還原氧化石墨烯/電活性聚醯胺複合材料之合成 90
4.4.6 代號說明 90
4.4.7 催化還原對-硝基苯酚 90
4.5 結果與討論 91
4.5.1 氧化石墨烯及還原氧化石墨烯之FTIR鑑定 91
4.5.2 氧化石墨烯及還原氧化石墨烯之Raman光譜鑑定 92
4.5.3 氧化石墨烯及還原氧化石墨烯之XRD鑑定 94
4.5.4 氧化石墨烯及還原氧化石墨烯之XPS鑑定 95
4.5.5 氧化石墨烯及還原氧化石墨烯之TGA鑑定 97
4.5.6 氧化石墨烯及還原氧化石墨烯之形貌鑑定 98
4.5.7 金/氧化石墨烯/電活性聚醯胺及金/還原氧化石墨烯/電活性聚醯胺複合材料之FTIR鑑定 99
4.5.8 金/氧化石墨烯/電活性聚醯胺及金/石墨烯/電活性聚醯胺複合材料之CV鑑定 100
4.5.9 金/氧化石墨烯/電活性聚醯胺及金/還原氧化石墨烯/電活性聚醯胺複合材料之XRD鑑定 101
4.5.10 金/氧化石墨烯/電活性聚醯胺及金/還原氧化石墨烯/電活性聚醯胺複合材料之XPS鑑定 102
4.5.11 金/氧化石墨烯/電活性聚醯胺及金/還原氧化石墨烯/電活性聚醯胺複合材料之TGA鑑定 104
4.5.12 金/氧化石墨烯/電活性聚醯胺及金/還原氧化石墨烯/電活性聚醯胺複合材料之形貌鑑定 105
4.5.13 金/氧化石墨烯/電活性聚醯胺及金/還原氧化石墨烯/電活性聚醯胺複合材料用於催化還原對-硝基苯酚之探討 108
4.6 結論 113
第五章 總結與未來展望 114
5.1 總結 114
5.2 未來展望 116
參考文獻 117

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