臺灣博碩士論文加值系統

本研究主要目的乃為探討改質之奈米零價鐵之製備及其處理鈷、鉻及銅廢水之效率，實驗部份分為奈米零價鐵與高嶺土合成出複合材料SiO2包覆於奈米零價鐵表面進行改質；合成高嶺土/奈米複合材料為利用高嶺土與硫酸亞鐵溶液於適當比例混合，在利用化學還原法製備合成出複合材料，並以四乙氧基矽烷(TEOS)為前驅物合成SiO2包覆奈米零價鐵，另以貴重儀器鑑定其表面形貌與化學結構，比較不同表面改質特性對處理鈷、鉻及銅廢水的效率及可能的反應機制。
由場發掃描式電子顯微鏡(FE-SEM)分析可知，經高嶺土摻雜於奈米零價鐵之複合材料，顯示團聚現象已明顯改善；經穿透式電子顯微鏡(TEM)分析結果顯示，可觀察單顆奈米零價鐵平均分散吸附於高嶺土表面，減少奈米零價鐵團聚情形。由X光繞射儀(XRD)分析結果可知，在2θ = 44.5°及64.62°為零價鐵之特徵峰，在2θ = 24.88、35.9、38.52、54.94及70.08°為高嶺土之特徵峰，符合鐵標準品及高嶺土之圖譜，並經化學分析電子光譜儀(ESCA)分析可知，表面以Fe及α-FeOOH為主，且α-FeOOH含量較多，高嶺土改質前後之奈米零價鐵比表面積分別為13.68及14.81 m2/g，且孔徑分布更均勻，可知改質奈米零價鐵表面積增加、分散性更佳。使用介面電位移分析，其改質前後等電位點(IEP)分別為7.7及6，較未改質奈米零價鐵更能分散及吸附陽離子金屬污染物。
以TEOS為SiO2的前驅物，製備SiO2包覆奈米零價鐵，由TEM分析可知，核心的奈米零價鐵外層包覆5-10 nm雲狀具孔洞之SiO2薄層，核心粒徑大小約50 nm，並未出現明顯團聚的現象，且包覆亦較均勻。以FE-SEM分析可知，包覆SiO2之奈米零價鐵外觀十分粗糙且有團聚成大小不一的塊狀結構，且無法觀察到內部粒子，與未包覆前的顆粒狀圓球明顯不同。以XRD分析可知，在2θ =44.96及65.36°為零價鐵的特徵峰，於22°出現其寬胖之特徵峰，其為包覆奈米零價鐵外層之無晶形SiO2。
改質前後奈米零價鐵粉與Co(II)、Cu(II)及Cr(VI)進行還原反應實驗中，由原子吸收光譜(AAS)數據結果顯示改質前後零價鐵可以有效地完全去除鈷、銅及鉻污染廢水，且改質後處理效果提高，由反應動力結果顯示奈米零價鐵對於污染物溶液為擬一階反應(pseudo-first-order)，處理鈷、銅及鉻污染廢水濃度越低，則吸附方程式越趨近線性。由FE-SEM及XRD結果顯示反應後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ESCA及XRD鑑定其氧化鐵為Fe3O4及α-FeOOH。吸附鉻之奈米零價鐵粉經由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Cr(VI)之奈米零價鐵粉微粒上之鉻還原成Cr(III)，及第一層Cr-O之配位數為3.61，鍵長為1.98 Å，結果與Cr(III)相近。

The main objectives of the present study were to prepare surface-modified zero-valent iron nanoparticles (SMZVINs) for the remediation of cobalt, copper and chromium ions from wastewater. Experimentally, synthesis of the material, identification and application to treat cobalt, copper and chromium contaminated wastewater were conducted. SMZVINs were prepared using kaolinite clay and coating silica nanofilms. The synthesized kaolinite supported zero valent iron nanoparticles was mixed with iron(II) sulfate heptahydrate in same mass ratio of kaolinite, after using the borohydride reduction method at room temperature and ambient pressure. Tetraethoxysilane (TEOS) was used as the precursors to synthesize SiO2/zero-valent iron nanocomposites for coating. Characterization of kaolinite /Fe(0) and SiO2/Fe(0) reacted with Co(II), Cu(II), and Cr(VI) contaminated wastewater were also investigated by TEM, FESEM, XRD, XPS, FTIR, BET N2 isotherms, and XANES/EXAFS techniques. In addition, this study was also carried out to provide information concerning the removal efficiencies and mechanism in the chemical reductive treatment processes for Co(II), Cu(II), and Cr(VI) wastewaters.
By FE-SEM and TEM analyses, The presence of kaolinite resulted in decreased aggregation of zero-valent iron nanoparticles, yielding composites with a iso-electric point (IEP) of 6. Kaolinite/Fe(0) has characteristic peaks of kaolinite and Fe(0) at 2θ = 24.88, 35.9, 38.52, 54.94, 70.08°, and 2θ = 44.5 and 64.62°, respectively analyzed by XRD. The surface area measured by BET N2 isotherms was 17 m2/g. From ESCA spectra, the main species on the surface of kaolinite/Fe(0) nanoparticles were Fe and α-FeOOH.
By using a TEOS as the precursor, SiO2/Fe(0) nanocomposites were synthesized. From TEM and SEM analyses, the core of SiO2/Fe(0) nanocomposite has a diameter around 50 nm and the shell of SiO2/Fe(0) nanocomposites relatively looses and possesses aperture structure. SiO2/Fe(0) nanocomposites have characteristic peaks of SiO2 and Fe(0) at 2θ = 22° and 2θ = 44.96° and 65.36° respectively analyzed by X-Ray diffraction.
SMZVINs reacted with Co(II), Cu(II), and Cr(VI) solutions and the concentrations of solutions determined by AAS decreased with increasing reaction times. Kinetics analyses from batch studies revealed that the removal of Co(II), Cu(II), and Cr(VI) from aqueous reaction with SMZVINs appeared to be a pseudo first-order with respect to metal contaminants. Metal-adsorbed Fe(0) nanoparticles were observed using FE-SEM and XRD and the comparison was found abnormally. It was possible that parts of Fe(0) nanoparticles were oxidized in the adsorption process. This study exemplifies the utilization of XRD and XPS to reveal the speciation and possible reaction pathway in a very complex adsorption and redox reaction process. Moreover, XANES spectra and EXAFS data also showed that Cr(VI) reduced to Cr(III). The Cr atoms in SMZVINs have the first shell of Cr-O bonding with a bond distance of 1.98 Å and a coordination number of 3.61.

目 錄
頁次
摘 要 II
ABSTRACT IV
誌 謝 VI
目 錄 I
圖 目 錄 VI
表 目 錄 XV
第一章 前言 1
第二章 文獻回顧 4
2.1 含鈷離子廢水簡介 4
2.1.1 鈷污染來源 4
2.1.2 鈷的簡介 7
2.1.3 鈷的污染危害 9
2.1.4 放射性鈷物質對生態環境之影響 10
2.2 鉻污染現況 13
2.2.1 鉻污染來源 13
2.2.2 鉻之性質 14
2.2.3 鉻污染危害 16
2.3 銅廢水簡介 18
2.3.1 銅污染來源 18
2.3.2 銅的簡介 19
2.3.3 銅對人體的作用 21
2.4 零價鐵處理技術簡介 22
2.4.1 奈米微粒 22
2.4.2 奈米材料性質 23
2.4.3 奈米粒子的表面效應 24
2.4.4 奈米鐵粒子的製備 28
2.4.5 奈米材料和技術的應用前景 32
2.4.6 鐵物質之簡介 34
2.4.7 奈米零價鐵之性質 37
2.4.8 奈米零價鐵之應用 41
2.4.9 電子轉移過程 49
2.5粒子表面改質及分散 53
2.5.1 改質與分散 53
2.5.2 核-殼結構複合材料簡介 54
2.5.3 分形理論 55
2.5.4 化學法分散奈米粉體 56
2.5.5 介面電位 59
2.6 磁性光觸媒之簡介 61
2.6.1 磁性光觸媒的製備 62
第三章 實驗方法與分析 67
3.1 實驗藥品 67
3.2 實驗儀器 68
3.3 實驗步驟 69
3.3.1 奈米零價鐵合成與改質 69
3.3.2 Fe(0)加入高嶺土實驗 71
3.3.3 以TEOS為前驅物合成SiO2/Fe(0)實驗 72
3.3.4 以TBT為前驅物合成TiO2/Fe(0)實驗 75
3.3.4 以TBT為前驅物合成TiO2/Fe(0)實驗 75
3.3.5 奈米零價鐵處理鈷、銅及鉻廢水實驗 77
3.4 分析方法 78
3.4.1 穿透式電子顯微鏡 78
3.4.2 場發掃描式電子顯微鏡 80
3.4.3 X光粉末繞射儀 82
3.4.4 界面電位儀 84
3.4.5 化學分析電子光譜儀 86
3.4.6 比表面積 88
3.4.7 同步輻射吸收光譜 90
3.4.8 原子吸收光譜 94
第四章 結果與討論 96
4.1 奈米零價鐵/高嶺土複合材料之合成 96
4.1.1 奈米零價鐵/高嶺土複合材料之晶相及表面分析 99
4.1.2 奈米零價鐵/高嶺土複合材料之比表面積及孔洞分析 111
4.2二氧化矽包覆奈米零價鐵之合成 115
4.2.1 SiO2/Fe(0)之晶相及外觀分析 116
4.2.2 二氧化矽包覆奈米零價鐵之比表面積及孔洞分析 125
4.3二氧化鈦包覆奈米零價鐵之合成 127
4.3.1 TiO2/Fe(0)之晶相及外觀分析 129
4.3.2 二氧化鈦包覆奈米零價鐵之比表面積及孔洞分析 141
4.4 Fe(0)、高嶺土/Fe(0)及SiO2/Fe(0)處理含鈷、銅及鉻廢水之分析 143
4.4.1 Fe(0)、高嶺土/Fe(0)及SiO2/Fe(0)處理含鈷、銅及鉻廢水實驗 143
4.4.2奈米零價鐵重複處理含鈷、銅及鉻廢水之實驗 155
4.4.3 改質前後奈米零價鐵處理含鈷廢水之pH、DO及ORP變化探討 157
4.4.4 Fe(0)、高嶺土/Fe(0)及SiO2/Fe(0)處理含鈷、銅及鉻廢水之表面分析 161
4.5 X光吸收邊緣結構性質分析 174
4.5.1 延伸細微結構X光吸收光譜性質分析 176
5.1 結論 178
5.2 未來研究方向 183
參考文獻 184
附錄A 199

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