本篇論文使用具有高比表面積的奈米碳材針對環境中的汙染物進行去除，並且將它與磁性奈米粒子結合，可以在外加磁場下收集分散在溶液中的複合材料。使用Hummer法合成氧化石墨(graphite oxide, GO)，將聚二烯丙基二甲基胺鹽酸鹽(PDDA)與氧化石墨混合後，再加入鐵離子以共沉澱法進行一步(one-pot)合成還原氧化石墨-氧化鐵奈米複合材料(RGO-Fe3O4 NPs)，其對芳香環類化合物和生物分子有良好吸附特性，並且能使用外加磁場回收，避免繁瑣的離心、沉澱等過程，作為一個快速及有效去除環境汙染物的材料。
一、 結合修飾聚山梨醇酯20之金奈米粒子和還原氧化石墨-氧化鐵奈米複合材料用來快速且有效去除環境水樣中的汞離子
本篇研究使用修飾聚山梨醇酯20之金奈米粒子(Tween 20-AuNPs) 作為吸附劑去除高鹽類基質中的有機汞和無機汞，並且以還原氧化石墨-氧化鐵奈米複合材料(RGO-Fe3O4 NPs)回收吸附完汞離子之Tween 20-AuNPs。聚山梨醇酯20是一種常見的保護試劑，讓檸檬酸鈉還原得到的金奈米粒子保持穩定分散在高鹽類基質溶液中，金奈米表面剩餘的檸檬酸根可以將Hg2+還原到Hg0並吸附在金奈米粒子表面，Hg0沉澱在金奈米表面接著形成金汞合金(Au-Hg amalgams)。利用RGO和Tween 20之間疏水性作用力(hydrophobic interaction)，加入RGO-Fe3O4 NPs收集分散在溶液中含Hg0的Tween 20-AuNPs，免去費時的離心和轉移過程，相較於已知以奈米材料為基礎來去除汞的方法，利用Tween 20-Au NPs可以快速(< 30分鐘)、高效率(> 99 %)、重複使用(>10次)在高鹽類基質、大pH值範圍下，不受其他金屬離子干擾選擇性的去除Hg2+、CH3Hg+、C2H5Hg+等。並且經由加熱使汞離子揮發後可以重複使用十次。
二、 合成還原氧化石墨-氧化鐵奈米複合材料用來快速去除環境汙染物：(1)亞甲基藍；(2)雙酚A；(3)油汙；(4)砷離子
此篇研究延續使用上篇研究的RGO-Fe3O4 NPs來分別針對亞甲基藍、雙酚A、砷離子、機油這幾種物質作去除。亞甲基藍(methylene blue, MB)和雙酚A(bisphenol A, BPA)都是含有芳香環類化合物，可以和RGO-Fe3O4 NPs上的RGO以π-π interaction的方式吸附到材料上，MB在鹼性條件下(pH 11)可以快速(< 30分鐘)被吸附，其最大吸附量為每克RGO-Fe3O4 NPs可以吸附62.9毫克MB，並且吸附完的RGO-Fe3O4 NPs可以經由溶劑清洗步驟重複使用十次；BPA則可在pH 4 - 9下快速(< 30分鐘)吸附到材料上，其最大吸附量為12.9 mg / g，吸附完的材料亦可以經由溶劑清洗重複使用四次；RGO會因為疏水性和親油性作用力選擇性吸附水中的機油，將RGO-Fe3O4 NPs均勻分散在機油中，施以外加磁場下可以將水面上的油汙隨著磁場方向移動來去除油污。(其重量比為RGO-Fe3O4 NPs：油 = 13606：1)；利用砷離子容易和鐵離子形成砷鐵錯合物，使用有較大比表面積的RGO-Fe3O4 NPs，可以在小於pH 11的環境下快速(< 10分鐘)去除As(III)及As(V)，其最大吸附量分別為7 mg / g和8 mg / g，並且可在真實環境水樣中去除，RGO和表面修飾的PDDA可以保護Fe3O4 NPs，避免材料因為氧化和聚集而減少吸附表面積。本研究中配合使用RGO和Fe3O4 NPs可以針對不同種類汙染物達到一個有效的去除，未來可以應用於工廠廢水、河川汙染、海洋漏油汙染等環境汙染防治議題上。

I. Combined Tween 20-stabilized Gold Nanoparticles and Reduced Graphite Oxide-Fe3O4
Nanoparticle Composites for Rapid and Efficient Removal of Mercury Species in
Environmental Water
This study describes a simple method for removing mercuric ions (Hg2+) from a high-salt matrix based on the use of Tween-20-stabilized gold nanoparticles (Tween 20-Au NPs) as Hg2+ adsorbents and composites of reduced graphite oxide and Fe3O4 NPs as NP collectors. Citrate ions adsorbed on the surface of the Tween 20-Au NPs reduced Hg2+ to Hg0, resulting in the deposition of Hg0 on the surface of the NPs and the formation of an Au–Hg amalgam. To circumvent time-consuming centrifugation and transfer steps, the Hg0-containing gold NPs were collected using reduced graphite oxide-Fe3O4 NP composites. Compared with the reported NP-based methods for removing Hg2+, Tween 20-Au NPs offered the rapid (within 30 min), efficient (> 99% elimination efficiency), durable (> 10 cycles), and selective removal of Hg2+, CH3Hg+, and C2H5Hg+ in a high-salt matrix, without the interference of other metal ions. This was attributed to the fact that the Tween 20-Au NPs were dispersed in a high-salt matrix, providing them with large surface to volume ratio to interact with Hg2+. The formation of graphite oxide sheets and reduced graphite oxide-Fe3O4 NP composites was demonstrated using X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, Fourier transform infrared spectrometry, and/or transmission electron microscopy. The mechanism of interaction between Tween 20-Au NPs and Hg2+ was studied using visible spectroscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy.
II. Synthesis of Ruduced Graphite Oxide-Fe3O4 Nanoparticle Composites for Rapid
Removal of Environmental Contaminants:(1)Methylene blue; (2)Bisphenol A; (3)Oil;
(4)Arsenic ions
Developing of a rapid, simple, efficient method for removing methylene blue, bisphenol A, oil and arsenic ion from aqueous media using reduced graphite oxide-Fe3O4 nanoparticle composites. The nanocomposites with both magnetic and good adsorption capacity have been one-pot synthesized via PDDA-modified and coprecipitation process. Here we demonstrated the potential environmental engineering application of this nanocomposite by taking organic dye and emerging contaminants, methylene blue and bisphenol A, as our model system. Methylene blue and bisphenol A are heterocyclic aromatic chemical compound, and adsorb on the surface of ruduced Graphite Oxide-Fe3O4 nanoparticle composites through strongly π-π interaction between aromatic ring structure and sp2 orbital. Reduced graphite oxide-Fe3O4 nanoparticle composites with hydrophobic but oleophilic coating, such as reduced graphite oxide, a selectivity oil-adsorbing material capable of floating on sea water is achieved. Because of the low density and the ability to absorb nonpolar liquids and oils, the nanomaterials allow to collect organic contaminants from the water surface. The hybrids show a high binding capacity for As(III) and As(V), whose presence in the drinking water in wide areas of South Asia has been a huge problem. The formation of As-Fe complex lead to a deposition of arsenic ion on the surface of nanocomposites. Their high binding capacity is due to the increased adsorption sites in the RGO-Fe3O4 NPs composites which occur by reducing the aggregation of bare magnetite. Since the composites show near complete (over 98.0%) arsenic removal within 10 μM, they are practically usable for arsenic separation from environmental water.

謝誌.........................................................................................................................i
中文摘要.................................................................................................................iii
英文摘要..................................................................................................................v
目錄.......................................................................................................................vii
圖表目錄..................................................................................................................x
縮寫表...................................................................................................................xiii
第一章 結合修飾聚山梨醇酯20之金奈米粒子和還原氧化石墨-氧化鐵奈米複合材料用來快
速且有效去除環境水樣中的汞離子
一、 前言…………………………………………………………………………...............…. 1
二、 實驗步驟………………………………………………………………................…....... 4
2.1 藥品與溶液配置…………………………………………...…………….......................… 4
2.2 儀器裝置………………………………………………................................................. 8
2.3 金奈米粒子製備方法……………………………..................…………………............. 11
2.4 合成還原氧化石墨-氧化鐵奈米複合材料.............................................................. 12
2.5 模擬還原氧化石墨形成...................................................................................... 14
2.6 汞離子去除過程................................................................................................ 15
三、 結果與討論.................................................................................................... 17
3.1 Hg2+去除機制之探討........................................................................................ 17
3.2 Hummer法合成之氧化石墨表面特徵鑑定............................................................. 23
3.3 還原氧化石墨-氧化鐵奈米複合材料表面特徵鑑定................................................. 25
3.4 模擬還原氧化石墨合成...................................................................................... 28
3.5 去除條件最適化與重複使用探討......................................................................... 33
3.6 對於其他離子干擾和真實樣品之探討.................................................................. 38
3.7 對汞物種最大吸附能力之探討............................................................................ 40
3.8 證實金汞合金之形成......................................................................................... 46
四、 結論............................................................................................................. 50
五、 參考資料....................................................................................................... 51
第二章 合成還原氧化石墨-氧化鐵奈米複合材料用來快速去除環境汙染物：(1)亞甲基藍；
(2)雙酚A；(3)油汙；(4)砷離子
一、 前言…………………………………………..…………………......………...........…... 60
二、 實驗步驟……………………………………………………………….................…..... 66
2.1 藥品與溶液配置................................................................................................ 66
2.2 儀器裝置………...............…………………………………………............................. 71
2.3 還原氧化石墨-氧化鐵奈米複合材料製備方法........................................................ 72
2.4 不同氧化鐵奈米粒子製備方法............................................................................ 72
2.5 樣品製備......................................................................................................... 73
三、 結果與討論.................................................................................................... 79
3.1.1 去除亞甲基藍之機制探討................................................................................ 79
3.1.2 探討pH值和反應時間對亞甲基藍吸附效果之影響............................................... 81
3.1.3 亞甲基藍最大吸附能力之探討......................................................................... 84
3.1.4 亞甲基藍重複使用能力和與其他材料比較之探討............................................... 87
3.2.1 去除雙酚A之機制探討.................................................................................... 90
3.2.2 探討pH值和反應時間對雙酚A吸附效果之影響................................................... 92
3.2.3 雙酚A最大吸附能力之探討.............................................................................. 95
3.2.4 雙酚A重複使用能力和不同材料去除能力比較之探討.......................................... 98
3.3.1 海上油汙去除之機制探討.............................................................................. 101
3.3.2 油汙去除能力之探討......................................................................................103
3.4.1 去除砷離子之機制探討................................................................................. 106
3.4.2 探討pH值和反應時間對砷離子吸附效果之影響................................................ 108
3.4.3 砷離子之最大吸附能力和恆溫吸附模式探討.................................................... 111
3.4.4 其他離子干擾以及真實樣品應用之探討........................................................... 115
3.4.5 有機砷離子去除和材料重複使用能力之探討.................................................... 118
四、 結論............................................................................................................ 123
五、 參考資料..................................................................................................... 124

第一章 結合修飾聚山梨醇酯20之金奈米粒子和還原氧化石墨-氧化鐵奈米複合材料用來快
速且有效去除環境水樣中的汞離子
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第二章 合成還原氧化石墨-還原氧化鐵奈米複合材料用來快速去除環境汙染物：(1)亞甲基
藍；(2)雙酚A；(3)油汙；(4)砷離子
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