工業排放的廢水，造成水中有機染劑的污染一直以來是個嚴重的問題，除了嚴重影響生活的環境還會對人體造成健康上的威脅。近年來水汙染議題越來越被重視，自然而然我們會希望用有效率的方式來處理這個問題。因此有了高級氧化處理法(advanced oxidation processes)，這種方式通常會使用O 3、 H2O2、 UV等無汙染的氧化劑配合催化劑產生羥基自由基(hydroxyl radical)與超氧化氫自由基(hydroperoxyl radical)將有機物或者染劑進行降解破壞，改善汙染問題。本實驗以化學沉澱法將溶液中的鐵離子和銅離子氧化還原製備出超順磁的雙金屬和金奈米粒子。透過X-ray 粉末繞射儀和以穿透式電子顯微鏡分析奈米粒子的特徵，活化過氧化氫，並使用感應偶合電漿質譜儀分析奈米粒子中所含金屬比例。接著以亞甲基藍(methylene blue)當作汙染物，並且改變奈米粒子中銅的比例，透過紫外光譜儀(Ultraviloet-visible spectroscopy)觀察在不同反應時間亞甲基藍的消色降解程度。在pH為4的反應條件下，反應60分鐘後，製備的雙金屬和金奈米粒子，我們將它命名為Fe-Cu-0.8消色程度超過95%，在動力學分析中，反應屬一級反應。接著測試製備出來的Fe-Cu-0.8是否對不同有機汙染物也能有效進行催化降解，因此選擇對硝基苯酚當作目標分子，採同一反應系統測試催化效果，並透過紫外光譜儀觀察不同時間對硝基苯酚的光譜情況。接下來找出最適合的反應條件，進行重複使用實驗，重複五次後催化效果還具有80%。製備出來的雙金屬合金具重複使用以及兼有磁性好回收的優點，此項技術用於處理受染料污染的汙水中，將來具有商業發展性。

Industrial dyes are an increasingly important class of wastewater pollutants that cause serious environmental and health issues. Such dyes, when left untreated result in chemical and biological changes to the aquatic environment, as well as being toxic to humans. Advanced Oxidation Processes (AOPs) involve more than one type of oxidation mechanism. These reactions accelerate production of the hydroxyl radical and hydroperoxyl radical, which are highly reactive and can degrade organic compounds and dyes. The AOP technique utilizes Fenton’s reagent, ultra violet (UV) radiation, and ozone (O3). In the first part of our experiment, we synthesized the bimetallic alloy Fe3O4/CuO, and used ICP-MS to monitor the Cu/Fe alloy ratio. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to characterize the structure of the nanoparticles. A superconducting quantum interference device (SQUID) confirmed the magnetic properties. X-ray photoelectron spectroscopy (XPS) was used to characterize the chemical state of the nanoparticle alloy constituents. We selected methylene blue (MB) as the target molecule to test the Fe-Cu-0.8 alloy in the presence of hydrogen peroxide while monitoring the reaction with UV-Vis spectroscopy. After 60 minutes, the Fe-Cu-0.8 alloy decolorized MB to 95% at pH 4. Kinetic analysis confirmed that this was a first order reaction. In the second part of the experiment, we determined that the Fe-Cu-0.8 alloy can also degrade p-Nitrophenol under the same reaction conditions. Finally, we determined the best conditions for reaction and repeated the experiment 5 times to confirm that the Fe-Cu-0.8 can be recycled. Our results suggest that the Fe-Cu-0.8 alloy may be a good candidate for AOP catalytic degradation of dyes and other organic pollutants.

目錄
論文審定書 i
摘要 ii
Abstract iii
圖目錄 vi
表目錄 viii
第一章 緒論 1
1-1奈米科技 1
1-2研究動機 3
第二章 儀器原理 4
2-1 紫外/可見光譜 4
2-1-1紫外/可見光譜(Ultraviolet-Visible Spectrometry,UV-Vis) 4
2-1-2 比爾定律(Beer’s Law) 5
2-1-3使用儀器與參數設定 7
2-2 X-ray 粉末繞射儀 7
2-2-1 X光粉末繞射 7
2-2-2 X-ray 繞射原理 8
2-2-3 使用儀器與參數設定 9
2-3穿透式電子顯微鏡 ( Transmission Electron Microscope, TEM ) 10
2-3-1 TEM工作原理 10
2-3-2 TEM成像機制 10
2-3-3 使用儀器與參數設定 11
2-4 分析儀器 11
第三章 製備不同比例的銅鐵合金對亞甲基藍降解的反應探討 13
3-1. 前言 13
3-2 文獻回顧 14
3-2-1 廢水處理方式 14
3-2-2 芬頓反應(Fenton reaction) 18
3-2-3 類芬頓反應(Fenton-like reactions) 18
3-2-4 染料(Dye) 19
3-2-5雙金屬合金 21
3-2-6磁性奈米粒子 22
3-3 實驗部分 24
3-3-1 實驗藥品 24
3-3-2 實驗步驟 24
3-4 實驗結果 26
3-4-1 氧化銅/氧化鐵雙金屬奈米粒子的應用和特徵分析 26
3-4-2 亞甲基藍降解測試 27
3-4-3 亞甲基藍降解結果與討論 29
3-4-4反應動力學分析(Kinetics of Fenton reaction) 33
3-4-5 Fe-Cu-0.8的特徵分析 35
3-4-6亞甲基藍的降解機制 41
3-5 結論 43
第四章 以雙金屬合金Fe-Cu-0.8透過高級氧化程序降解對硝基苯酚 44
4-1. 前言 44
4-2. 文獻回顧 44
4-2-1 對硝基苯酚 44
4-3 實驗部分 45
4-3-1 實驗藥品 45
4-3-2 實驗步驟 46
4-4 實驗結果 47
4-4-1對硝基苯酚催化測試 47
4-4-2反應動力學分析(Kinetics of Fenton reaction) 53
4-4-3 Fe-Cu-0.8降解對硝基苯酚重複使用性探討 55
4-4-4對硝基苯酚可能的降解反應機制 55
4-4-5結論 57
第五章 結論 58
參考文獻 59


 
圖目錄
圖2-1 電磁波頻譜範圍 4
圖2-2 UV光譜電子躍遷示意圖 5
圖2-3 X光粉末繞射偵測過程 7
圖2-4二維XRD圖形 8
圖2-5布拉格繞射示意圖 9
圖3-1為高級氧化程序的優缺點 15
圖3-2 廢水處理的相關技術和優缺點 17
圖3-3亞甲基藍分子結構 20
圖3-4亞甲基藍UV-Vis吸收特徵圖 21
圖3-5 氧化銅奈米粒子製備示意圖 25
圖3-6氧化銅奈米粒子製備示意圖 25
圖3-7氧化銅/氧化鐵雙金屬合金 26
圖3-8亞甲基藍消色實驗示意圖 27
圖3-9透過不同催化劑進行亞甲基藍的降解(a)H202/MB(b)CuO (c)Fe3O4 (d)Fe-Cu-0.02 (e)Fe-Cu-0.08 (f)Fe-Cu-0.32 (g)Fe-Cu-0.8 (h)CuO/Fe3O4 28
圖3-10不同合金在pH4，3.5% H2O2進行催化效率的比較 30
圖3-11透過不同催化劑進行亞甲基藍的降解(a)H202/MB(b)CuO (c)Fe3O4(d)Fe-Cu-0.8 32
圖3-12不同合金在pH4，3.5% H2O2進行催化效率的比較 32
圖3-13以lnC/C0對時間(min)作圖，(a)CuO(b)Fe3O4(c)Fe-cu-0.02(d)Fe-Cu-0.08(e)Fe-Cu-0.32(f)Fe-Cu-0.80(g)CuO/Fe3O4 34
圖3-14實驗所製備的氧化鐵奈米粒子XRD繞射圖譜 36
圖3-15實驗所製備的Fe-Cu-0.8奈米粒子XRD繞射圖譜 37
圖3-16(a)Fe-Cu-0.8奈米粒子TEM (b)(c)Fe-Cu-0.8奈米粒子HRTEM 37
圖3-17 Fe-Cu-0.8的Cu 2p的光電子光譜圖(a)CuO(b)反應前Fe-Cu-0.8(c)反應後Fe-Cu-0.8 38
圖3-18 Fe-Cu-0.8的Fe 2p的光電子光譜圖(a)Fe3O4(b)反應前Fe-Cu-0.8(c)反應後Fe-Cu-0.8 39
圖3-19殘留在Fe-Cu-0.8表面S 2p訊號圖譜 40
圖3-20 Fe-Cu-0.8磁滯曲線圖 41
圖3-21亞甲基藍的降解機制 42
圖4-1為對硝基苯酚結構 45
圖4-2降解PNP的反應過程示意圖 46
圖4- 3PNP降解UV-VIS圖譜 47
圖4-4透過不同催化劑進行對硝基苯酚的催化(a)H202/MB(b)CuO (c)Fe3O4 (d)Fe-Cu-0.8 48
圖4-5不同合金在pH4.9，0.1 % H2O2對PNP進行催化效率的比較 49
圖4-6改變不同反應環境條件參數，觀察Fe-Cu-0.8對PNP催化降解的影響 50
圖4-7在不同反應條件下降解有機分子PNP對時間做圖 51
圖4-8以lnC/C0對時間(min)作圖，在不同反應條件下降解有機分子PNP對時間做圖 54
圖4-9 Fe-Cu-0.8重複使用性探討 55
圖4-10 PNP可能降解的機制圖 56

 
表目錄
表3-1透過不同催化劑以高級氧化處理法的方式氧化不同的有機汙染物 17
表3-2實驗所需要品列表 24
表3-3雙金屬合金中所含銅與鐵百分比 27
表3-4 Kinetics v.s. dynamics 35
表4-1實驗所需要品列表 46
表4- 2 Fe-Cu-0.8降解對硝基苯酚反應前後pH值變化 52
表4-3 Kinetics v.s. dynamics 54

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