近年來，國內受高污染硝酸鹽/亞硝酸鹽類之養殖業及重金屬鉻污染之水體十分嚴重，造成人體危害及環境之衝擊。因此，本研究之主要目的是探討利用化學還原法製備奈米零價鐵微粒，藉由精密光譜分析儀器檢測奈米零價鐵微粒吸附含氮鹽類及含鉻溶液後之變化與結構分析，並利用聚乙二醇(PEG)保護膜來增加零價鐵之還原污染物之效率。
實驗中，由穿透式電子顯微鏡(TEM)分析可明顯發現，在奈米零價鐵微粒表面上有5~10 nm之PEG高分子膜。經由同步輻射XANES分析奈米零價鐵粉對於處理硝酸鹽/亞硝酸鹽是將其還原為氮氣，零價鐵經氧化反應由零價轉為三價；奈米零價鐵粉對於六價鉻是進行還原反應將其還原成三價鉻；表示表面吸附及氧化還原反應，只在奈米零價鐵粉表面上同時進行。吸附動力結果顯示奈米零價鐵對於六價鉻是為擬一階反應(pseudo-first-order)，處理污染水體濃度越低，則吸附方程式越趨近線性，而奈米零價鐵對於處理硝酸鹽/亞硝酸鹽則以二階反應使其線性迴歸。奈米零價鐵還原硝酸鹽及亞硝酸鹽之污染水溶液；硝酸鹽水溶液系統之pH值將會維持在8~9左右；亞硝酸鹽水溶液則維持在8.5~9.5左右。硝酸鹽類降解反應過程中，pH值為其重要之控制因子，低pH值環境下有助於奈米零價鐵粉對硝酸鹽降解速率之提昇。經由陰離子層析儀(IC)數據結果顯示每克零價鐵粉可分別還原100~300 ppm硝酸鹽及150~400 ppm亞硝酸鹽污染水體。由原子吸收光譜(AAS)數據結果顯示零價鐵可以有效地完全去除六價鉻污染水體。掃描式電子顯微鏡(FE-SEM)及X光粉末繞射儀(XRPD)結果顯示吸附鉻之奈米零價鐵粉微粒表面可能為紅褐色氧化鐵，結構成鬆散狀。經由X光吸收近邊緣結構(XANES)及延伸X光吸收精細結構(EXAFS)光譜顯示，吸附六價鉻之奈米零價鐵粉微粒上之鉻還原成Cr2O3；相反地，還原硝酸鹽及亞硝酸鹽後之奈米零價鐵粉微粒則氧化成Fe2O3。此外，亦利用共振非彈性X光散射光譜(RIXS)分析，可以更精確瞭解反應前後零價鐵微粒中Fe元素之價數介於2~3間。由於奈米零價鐵粉對於受鉻及含氮鹽類污染物之去除具有高活性、效果佳及且已有初步成效，故未來應用於重金屬污染場址之現址復育（in-situ remediation）技術。本研究亦是典型應用同步輻射光源及原子級分析光譜，研究奈米零價鐵微粒吸附受毒性鉻金屬及硝酸鹽/亞硝酸鹽污染水體，在其表面氧化還原反應之實例。

In recent years, chromium, nitrate, and nitrite contaminants are very serious problems in Taiwan. Chromium, nitrate or nitrite species are known to be toxic and carcinogenic, site remediation is necessarily required in order to reduce the risk to human races and ecosystems. Therefore, the main objectives of the present study were to investigate chemical reduction of chromium, nitrate or nitrite species by nanoscale zero-valent iron (ZVI) in aqueous solution and related reaction kinetics or pathways. Nanophase zero-valent iron powders could be enhanced the efficiency of reduction by adding polyethylene glycol (PEG ) nanofilms.
Experimentally, ZVI nanoparticles of this study were prepared by borohydride reduction method at room temperature and ambient pressure. At the surface of ZVI nanoparticles there coated about 5~10 nm film of polyethylene glycol measured by TEM. The existence of Cr species on the Fe(0) nanoparticles was also confirmed by XANES. It was also found that mainly Cr(III) with a small amount of Cr(0) was adsorbed on the Fe(0) nanoparticles. Kinetics analysis from batch studies revealed that the removal of Cr(VI) from aqueous reaction with nanoscale Fe(0) appeared to be a pseudo first-order with respect to contaminant substrates. The kinetic model of nitrate/nitrite reduction by nanoscale Fe(0) powder is proposed as second-order kinetic equation. The results showed that the degradation reaction of nitrate/nitrite was significantly effected by pH values. The faster rates of nitrate/nitrite reduction were shown at lower pH. The Cr-adsorbed Fe(0) nanoparticles measured by FE-SEM and XRD were abnormally incompact, it was possible that Fe(0) nanoparticles were, to some extent, oxidized in the adsorption process. This work exemplifies the utilization of XANES, XRD, and XPS to reveal the speciation and possible reaction pathway in a very complex adsorption and redox reaction process. EXAFS spectra showed Cr(VI) reduce to Cr2O3 and nitrate/nitrite reduce to N2 while oxidizing the Fe(0) to Fe2O3 electrochemically. In addition, by using resonant inelastic X-ray scattering (RIXS) technique, the fine valent of iron between 2 and 3 may be further investigated. It is also very clear that decontamination of chromium, nitrate or nitrite species in groundwater via the in-situ remediation with nanophase Fe(0) permeable reactive barriers would be environmentally attractive in the future.

摘 要 I
Abstract III
目 錄 V
圖 目 錄 X
表 目 錄 XV
第一章 前言 1
第二章 文獻回顧 4
2.1 鉻污染現況 4
2.1.1 鉻污染來源 4
2.1.2 鉻之性質 5
2.1.3 鉻污染危害 7
2.1.4 傳統鉻處理技術 9
2.2 含氮鹽類廢水簡介 11
2.2.1 水體中氮的型態 11
2.2.2 氮循環 12
2.2.3 水體中氮的管制量及相關法規 14
2.2.4 氮的分析方法 15
2.3 零價鐵處理技術的緣起與發展 16
2.3.1 零價鐵處理技術的緣起 17
2.3.2 零價鐵處理技術對去除鉻污染物上的應用 18
2.3.3 反應牆形式之地下水整治技術 27
2.4 奈米零價鐵之簡介 37
2.4.1 奈米微粒 37
2.4.2 奈米材料性質 38
2.4.3 奈米粒子的表面效應 39
2.4.4 奈米粒子的製備 42
2.4.5 奈米材料和技術的應用前景 43
2.4.6 鐵物質種類 45
2.4.7 奈米零價鐵製備方法 46
2.4.8 奈米零價鐵微粒 47
2.4.9 零價鐵還原鉻之反應式 50
2.5 聚乙二醇簡介 51
2.5.1 聚乙二醇性質 51
2.5.2 聚乙二醇應用 51
2.6 吸附模式 53
2.6.1 吸附理論 53
第三章 實驗方法與分析 56
3.1 實驗藥品 56
3.2 實驗器材 57
3.3 實驗步驟 58
3.3.1 合成奈米零價鐵 58
3.3.2 批次式試驗 60
3.3.3 連續式管柱試驗 62
3.3.4 PEG包覆溶解速率試驗 64
3.4 分析方法 65
3.4.1 穿透式電子顯微鏡 65
3.4.2 場發掃描式電子顯微鏡 67
3.4.3 原子吸收光譜 69
3.4.4 X光粉末繞射儀 71
3.4.5 比表面積 73
3.4.6 同步輻射吸收光譜 76
3.4.6.1 同步輻射光吸收實驗 76
3.4.6.2 實驗方法與步驟 78
3.4.6.3 實驗數據分析 79
3.4.7 共振非彈性X光散射 81
3.4.8 化學分析電子光譜儀 85
3.4.9 離子層析儀 87
3.4.10 總有機碳分析 90
第四章 結果與討論 93
4.1 奈米零價鐵粉合成及性質分析 93
4.1.1 奈米零價鐵粉之合成 93
4.1.2 奈米零價鐵粉之性質分析 95
4.2 聚乙二醇包覆奈米零價鐵粉之水中溶解速率分析 101
4.2.1 聚乙二醇包覆奈米零價鐵粉之膜厚及特性分析 101
4.2.2 聚乙二醇包覆奈米零價鐵粉之水中溶解速率計算 105
4.3 奈米零價鐵粉處理受鉻及含氮鹽類水體之吸附動力學分析 107
4.3.1 一階反應速率常數 107
4.3.2 一階反應之半衰期 112
4.3.3 奈米零價鐵粉還原鉻之動力學 113
4.3.4 硝酸鹽與亞硝酸鹽之動力學比較 117
4.3.5 電化學反應式之驗證 122
4.4 連續式管柱實驗數據分析 124
4.4.1 處理鉻污染水體管柱實驗數據分析 124
4.4.2 處理硝酸鹽污染水體管柱實驗數據分析 126
4.5 奈米零價鐵粉處理受鉻及含氮鹽類水體後之性質分析 128
4.5.1 FE-SEM性質分析 128
4.5.2 XPRD性質分析 130
4.5.3 XPS/ESCA性質分析 134
4.5.4 X光吸收邊緣結構性質分析 136
4.5.5 延伸細微結構X光吸收光譜性質分析 149
4.5.6 共振非彈性X光散射光譜分析 160
第五章 結論及未來研究方向 163
5.1 結論 163
5.2 未來研究方向 166
參考文獻 167
附錄A 奈米零價鐵粉處理鉻污染水體之數據結果 178
附錄B 奈米零價鐵粉處理硝酸鹽污染水體之數據結果 182
附錄C 奈米零價鐵粉處理亞硝酸鹽污染水體之數據結果 187
附錄D 聚乙二醇包覆奈米零價鐵粉之水中溶解數據結果 192

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