近年來奈米零價鐵在環境復育領域被廣泛的應用。此零價金屬具有低毒性、豐富性以及適當的電位可用來進行化學還原反應。然而奈米零價鐵的鐵磁性容易引起顆粒的嚴重聚集，使其移動性和反應性降低。近年來利用固態載體修飾奈米零價鐵為常見的技術之一，目的是為了要改善其反應活性。本篇研究將亞鐵離子吸附在氧化石墨烯上，之後用硼氫化鈉直接將材料還原成零價鐵複合還原石墨烯(rGO-Fe)。利用調控鐵前驅物和氧化石墨烯的重量比例，就能合成出均勻分散的奈米零價鐵。本研究的奈米零價鐵其顆粒尺寸為44.1nm，在三氯乙烯的降解反應下，其擬一階反應動力常數(kobs)為9.40×10-3 h-1, 比未經修飾的零價鐵高出3倍。因為雙金屬系統具有協同效應現象，所以加入共同金屬離子可以大大的提升零價鐵的反應活性。添加1.877 mM的金屬鎳離子和0.105 mM的金屬鈀離子於反應系統中，其三氯乙烯降解擬一階反應速率常數為分別為5.89和 53.6 h-1 ，皆大於單純的rGO-Fe奈米複合材料( 9.40×10-3 h-1)。此結果證實rGO-Fe複合材料在污染物水處理的效果的確優異。它的高反應活性和大的比表面積使之在環境領域運用上頗具潛力，並值得開發成多功能材料。

Nanoscale zerovalent iron (nZVI) has been widely used in environmental remediation. It has low toxicity, abundance in the world, suitable potential for triggering the reduction make it a promising material in decades. However, the ferromagnetism of ZVI nanoparticles leads to aggregation, causing low reactivity and mobility. In recent years, using solid supports for nZVI is one of the methods enhancing its reactivity. In this study, a facile approach for the synthesis and immobilization of ZVI nanoparticles onto reduced graphene oxide (rGO) have developing by adding NaBH4 as reducing agent. By adjusting the weight ratio between iron precursors and graphene oxide, we can purchase the well-dispersed ZVI nanoparticles on reduced graphene oxide. In this study, the diameter of particles of rGO-Fe nanocomposites was about 44.1 nm. Its pseudo-first rate constant (kobs) of TCE degradation can reach to 9.40×10-3 h-1, which was 3 times higher than conventional ZVI. Due to synergetic effect, adding second metal ions can significantly enhanced the reactivity of rGO-Fe nanocomposites. The kobs for TCE degradation were 5.89, and 53.6 h-1 at 1.877 mM Ni(II), 0.105 mM Pd(II). Both of them are much higher than rGO-Fe nanocomposites alone ( 9.40×10-3 h-1). The result obtained in this study proving that immobilization of ZVI nanoparticles on reduced graphene oxide is successful in water treatment. Its high reactivity and large surface area make it have potential developing in multifunctional use in environmental application.

第一章 簡介 1
1.1. 前言 1
1.2. 研究動機 2
1.3. 研究目的 3
第二章 文獻回顧 4
2.1. 氯化有機物 4
2.2. 奈米零價鐵 5
2.2.1. 奈米零價鐵的特性 5
2.2.2 奈米零價鐵的水處理和反應機制 7
2.2.3. 零價鐵與貴金屬之雙金屬奈米顆粒 8
2.2.4. 固態載體修飾奈米零價鐵之複合材料 10
2.3. 石墨烯修飾零價鐵或鐵氧化物在環境復育之應用 11
第三章 研究方法 14
3.1.實驗架構 14
3.2. 試劑與材料 15
3.3. 氧化石墨烯(graphene oxide)合成方法 16
3.4. 零價鐵與還原石墨烯的複合材料 17
3.5. 製備無氧水 19
3.6. 零價鐵與還原石墨烯的複合材料在不同濃度Ni2+、Pd2+之分析 19
3.7. 特性鑑定 19
3.7.1. X光粉末繞射儀 (X-ray Powder Diffractometer, XRD) 21
3.7.2. 拉曼散射光譜(Raman spectroscopy) 21
3.7.3. 比表面積分析儀 (Specific surface area & pore size distribution analyzer, BET) 22
3.7.4. 穿透式電子顯微鏡 (Transmission Electron Microscope, TEM) 23
3.7.5. 電子能譜儀 (X-ray Photoelectron Spectrometer, XPS) 23
3.7.6. 電子能譜儀 (Electron Probe X-Ray Microanalyzer, EPMA) 24
3.8 三氯乙烯還原脫氯批次實驗 25
3.8.1. 分析方法 26
第四章 結果與討論 28
4.1. 氧化石墨烯特性鑑定 28
4.1.1 XPS官能基分析 28
4.1.2 石墨氧化前後結晶性探討 29
4.1.3 石墨氧化前後Raman光譜探討 30
4.2. 氧化石墨烯吸附亞鐵離子之探討 32
4.3. 零價鐵與氧化石墨烯之複合材料鑑定 33
4.3.1 零價鐵、氧化石墨烯和其複合材料之形貌、晶相、顆粒之探討 33
4.3.2 不同比例之零價鐵與還原石墨烯複合材料之形貌、晶相、顆粒之探討 35
4.3.3 零價鐵與還原石墨烯之XPS鍵結情形 37
4.4 零價鐵與氧化石墨烯複合材料在不同金屬離子溶液中特性鑑定 44
4.4.1 rGO-Fe在不同濃度鎳離子(Ni2+) 溶液下之材料鑑定 44
4.4.2 rGO-Fe在不同濃度鈀離子(Pd2+) 溶液下之材料鑑定 64
4.5. 各材料對三氯乙烯還原催化反應效率之探討 81
4.5.1. 零價鐵複合還原石墨烯降解效率之探討 81
4.5.2. 不同零價鐵含量複合還原石墨烯降解效率之探討 85
4.6. 共同金屬離子對rGO-Fe複合材料催化三氯乙烯反應之影響 89
4.6.1. 不同濃度Ni2+下零價鐵複合還原石墨烯降解效率之探討 90
4.6.2. 不同濃度Pd2+下零價鐵複合還原石墨烯降解效率之探討 94
4.7. 電化學特性測試 98
第五章 結論 101
5.1. rGO-Fe複合材料的製備 101
5.2. rGO-Fe複合材料對三氯乙烯的還原脫氯反應 101
第六章 參考文獻 103

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