臺灣博碩士論文加值系統

本研究利用水熱法合成KIT-6，藉由溫度的改變合成出不同孔徑的KIT-6，並據以複製出表面積可達1155 m²/g之有序中孔碳CMK-8。並將Pt、Ag、Au、PtSnO2、PtAg前驅物以浸漬法附載於CMK-#孔洞內製備成複合材料。其中，CMK-#為CMK系列中孔碳材。應用於對硝基苯酚(4-nitrophenol, 4-NP)還原成對胺基苯酚(4-aminophenol, 4-AP)，並觀察添加不同材料(Ag、SnO2)於Pt/CMK-8催化劑對於催化還原性能的影響。並透過比表面積分析儀(BET)、掃描式電子顯微鏡(FE-SEM)、場發射穿透式電子顯微鏡(HR-TEM)、高解析X光繞射儀(XRD)、X射線光電子能譜儀(XPS)對奈米複合材料催化劑進行結構組成和性質分析。採用紫外光/可見光光譜儀(UV-vis)即時監控對硝基苯酚(1mM)還原對胺基苯酚的反應過程與時間的關係。研究表明，PtH/CMK-8只需要4分鐘即可完成整個反應過程。

利用不同的還原法分別命名為PtB/CMK-8(硼氫化納還原法)與PtH/CMK-8(氫氣還原法)，其中以PtH/CMK-8(氫氣還原法)所合成的鉑粒子粒徑最小且不會發生團聚現象。為了降低鉑的使用量，因此利用銀(Ag)金屬來參雜，銀比例越多，加快了還原速率。如果改用金屬氧化物(SnO2)參雜，Pt5Sn15中過量的SnO2團聚造成鉑催化活性的降低，導致10分鐘才能完成還原反應。將Pt5Ag15此比例添加於不同類型之中孔碳(CMK-3、CMK-5、CMK-9)，循環催化效果非常穩定，Pt5Ag15/CMK-3僅需要30秒就可以完成還原反應。根據不同催化劑的所需的還原反應時間做總結，可以得出Pt5Ag15/CMK-3>Pt5Ag15/CMK-8> Pt5Ag15/CMK-5> Pt5Ag15/CMK-9> Pt10Ag10/CMK-8> Pt15Ag5/CMK-8> Pt15Sn5/CMK-8>Pt/CMK-8>Pt10Sn10/CMK-8=Ag/CMK-8>Au/CMK-8>Pt5Sn15/CMK-8

KIT-6 was synthesized by hydrothermal method to synthesize KIT-6 with different pore sizes by changing the temperature. However, the specific surface area decreased with the increase of temperature. The ordered mesoporous carbon CMK-8 was replicated by KIT6-40°as a template. The surface area was 1155 m2/g, and the platinum precursor was prepared in the pore cavity of CMK-8 by impregnation. It is applied to the reduction of p-nitrophenol (4-nitrophenol, 4-NP) to p-aminophenol (4-aminophenol, 4-AP), and the effects of the addition of different materials (Ag, SnO2) on the catalytic reduction performance of Pt/CMK-8 catalysts, and through specific surface area analyzer (BET), scanning electron microscope (FE-SEM), field emission penetrating electron display The structure and properties of nanocomposite catalysts were analyzed by micromirror (HR-TEM), high analytical X light diffraction (XRD) and X ray photoelectron spectroscopy (XPS). The relationship between the reaction process and time of the reduction of p-nitrophenol (1mM) with p-nitrophenol (1mM) was monitored by ultraviolet light / light spectrometer (UV-vis). The study showed that PtH/CMK-8 It takes only 4 minutes to complete the whole reaction process.

PtB/CMK-8 (borohydride reduction method) and PtH/CMK-8 (hydrogen reduction method) are named respectively by different reduction methods, in which the particle size of platinum particles synthesized by PtH/CMK-8 (hydrogen reduction method) is the smallest and no agglomeration occurs. In order to reduce the use of platinum, the amount of silver (Ag) metal is mixed,the more the proportion of silver, the rate of reduction is accelerated.. If the metal oxide (SnO2) is used, the excess SnO2 reunion in Pt5Sn15 causes a reduction in the catalytic activity of the platinum catalyst, resulting in the reduction of the reduction reaction in 10 minutes. The ratio of Pt5Ag15 is added to different types of mesoporous carbon (CMK-3, CMK-5, CMK-9),and the catalytic effect is very stable and Pt5Ag15/CMK-3 takes 30 seconds. The reduction reaction can be completed. The reduction reaction can be completed. According to the reduction reaction time of different catalysts, it can be concluded that Pt5Ag15/CMK-3>Pt5Ag15/CMK-8>Pt5Ag15/CMK-5>Pt5Ag15/CMK-9>Pt10Ag10/CMK-8>Pt15Ag5/CMK-8>Pt15Sn5/CMK-8>Pt/CMK-8>Pt10Sn10/CMK-8=Ag/CMK-8>Au/CMK-8>Pt5Sn15/CMK-8.

摘要 3
Abstract 5
目錄
第一章 緒論 26
1-1 前言 26
1-2 研究動機及目的 27
第二章 文獻回顧 29
2-1孔洞材料簡介 29
2-2中孔二氧化矽介紹 33
2-2-1中孔KIT-6介紹 36
2-2-2中孔KIT-6合成機制 36
2-3中孔碳發展歷史 38
2-3-1中孔碳合成機制 39
2-3-2中孔碳附載金屬方法介紹 42
2-4中孔碳材料CMK-n 42
2-4-1 CMK-8介紹 45
2-4-2奈米鉑負載碳製備方法 46
2-4-3 CMK-8/Pt合成機制 48
2-5附載金屬之中孔碳在催化劑之應用 48
2-5-1燃料電池 49
2-5-2 超級電容 52
2-5-3感測器 53
2-5-4 氣體吸附 54
2-5-5 水中汙染物吸附與催化還原 56
2-6對硝基苯酚的介紹 59
2-7 奈米金屬對於4-NP的還原 60
第三章 實驗方法及步驟 64
3-1實驗藥品 66
3-2 實驗方法 68
3-2-1 中孔二氧化矽KIT-6製備 68
3-2-2中孔碳材CMK-8製備 70
3-2-3中孔奈米複合材料Pt/Au/Ag-CMK-8製備 72
3-2-4中孔奈米複合材料Pt/Ag-CMK-8製備 75
3-2-5中孔奈米複合材料Pt/SnO2-CMK-8製備 76
3-2-6催化反應 79
3-3分析設備 80
3-3-1比表面積分析儀(Brunauer-Emmett-Teller specific surface area analyzer, BET) 80
3-3-2場發射穿透式電子顯微鏡(High Resolution Transmission Electron Microscope, HR-TEM ) 83
3-3-3掃描電子顯微鏡(Scanning Electron Microscope:FE-SEM) 84
3-3-4 X射線光電子能譜學(X-ray photoelectron spectroscopy, XPS ) 85
3-3-5高解析X光繞射儀(High Resolution X-ray Diffractometer, HRXRD) 86
3-3-6紫外光-可見光光譜儀(UV-Vis spectrophotometer) 87
第四章 結果與討論 88
4-1 水熱溫度對KIT-6材料孔洞特性之影響 88
4-2 CMK-8的合成與鑑定 94
4-3 還原方式對Pt/CMK-8之微觀特性之影響 98
4-4 鍛燒溫度與時間對鉑奈米粒子的影響 98
4-5 Au/CMK-8之結構特性 112
4-6 Ag /CMK-8之結構特性 118
4-7 催化還原對-硝基苯酚(4-NP) 123
4-8 PtAg/CMK-8雙金屬合金對硝基苯酚的催化還原 130
4-9 PtSnO2/CMK-8催化劑對硝基苯酚的催化還原 142
4-10 PtAg/CMK-# (CMK-3、CMK-5、CMK-8、CMK-9) 對硝基苯酚催化還原的影響 153
第五章 結論 170
參考文獻 172

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