臺灣博碩士論文加值系統

本研究主要係取兩種程序特點，以達到相乘（synergy）之效果，將二氧化鈦（TiO2）與氧化石墨烯（graphene oxide, GO）利用電漿輔助塗佈方式，將材料固定於過濾膜上製成複合膜，減少二氧化鈦與氧化石墨烯回收的困擾，並結合UV/光催化方式處理含酚或染料有機廢水產生光降解作用，以提高光催化之效率。實驗使用商用型Millipore聚偏二氟乙烯（PVDF）疏水膜（平均孔徑0.45μm、平均厚度125μm），主要因聚偏二氟乙烯耐酸性佳及薄膜支撐力佳。利用不同重量百分比進行複合膜製備，二氧化鈦與氧化石墨烯之間的分散性會影響其光降解效率及電子傳導速率，利用X光繞射儀、X光電子能譜儀、拉曼光譜儀、傅立葉紅外線光譜儀、場發射掃描式電子顯微鏡進行材料分析。並將PVDF-g-PAA-GO/TiO2複合膜，使用功率100-W UV降解酚及甲基藍溶液，發現降解效率為 75%＞50%＞25%；即氧化石墨烯含量對於二氧化鈦在降解效率提升有一定幫助，並利用HPLC進行分析有機物濃度變化，以探討其光降解速率。

In this study, Two nanoscale materials, Titanium dioxide（TiO2） and graphene oxide（GO）, were used to achieve the synergy effect because of their characterizations. Commercial Millipore polyvinylidene fluoride （PVDF） hydrophobic membrane was used due to its excellent acid resistance and support the nanomaterials. TiO2 and GO were immobilized on a commercial Millipore polyvinylidene fluoride（PVDF） hydrophobic membrane by the method of Plasma-Assisted Coating. It showed that the UV/photocatalytic treatment with the PVDF-g-PAA-TiO2/GO membrane enhanced the photocatalytic efficiency of the photocatalyst. A vary of the composite of TiO2 and GO immobilized on PVDF membrane had been used for samples. The characterization of PVDF-g-PAA-TiO2/GO membrane was analyzed by X-ray diffraction（XRD）, X-ray photoelectron Spectrometer （XPS）, Raman spectroscopy, Fourier infrared spectrometer （FTIR） and field emission scanning electron microscope（FE-SEM）. The time constant of organic compound in a variety of concentrations analyzed by high performance liquid chromatography（HPLC） following a direct proportionality with the photo-degradation rate constant in different samples. The treatment with PVDF-g-PAA-TiO2/GO membrane marked a promising result in the degradation of phenol or dyestuff organic wastewater at 100-W UV followed by phenol and methylene blue solution. The results reveal the degradation rate: 75%> 50%> 25% in different samples.

指導教授推薦書
口試委員會審定書
致謝 iii
中文摘要 iv
Abstract v
目錄 vii
圖目錄 xi
表目錄 xv
符號說明 xvii
第一章 緒論 1
1.1 研究緣起 1
1.2 研究動機與目的 1
1.3 研究流程 4
第二章 文獻回顧 5
2.1 廢水處理基礎理論 5
2.2 聚偏二氟乙烯薄膜之特性 7
2.3 二氧化鈦 7
2.3.1 二氧化鈦光觸媒光催化原理 12
2.3.2 二氧化鈦反應機制 13
2.3.3 光催化動力學 15
2.4 石墨烯 18
2.4.1 石墨烯性質介紹 18
2.4.2 石墨烯的製備 19
2.5 石墨烯/二氧化鈦複合物 21
2.5.1 石墨烯/二氧化鈦複合物性質介紹 21
2.5.2 石墨烯/二氧化鈦複合物反應機制 22
2.5.3 石墨烯/二氧化鈦複合物的製備 23
2.6 酚 27
2.6.1 酚性質介紹 27
2.6.2 酚的危害性 28
2.6.3 光觸媒對酚降解 29
2.7 甲基藍 30
2.7.1 甲基藍性質介紹 30
2.7.2 光觸媒對甲基藍降解 31
2.8 電漿 32
2.8.1 大氣電漿 32
2.8.2 表面改質與塗佈 34
2.8.3 丙烯酸性質介紹 36
2.8.4 斷鏈轉移 38
第三章 實驗部分 40
3.1實驗藥品與儀器 40
3.1.1 實驗藥品 40
3.1.2 實驗儀器 41
3.1.3 氣旋式大氣電漿系統 43
3.1.4 光降解反應系統 46
3.2 複合膜製備 51
3.2.1 溶膠凝膠法製備二氧化鈦 51
3.2.2 製備氧化石墨烯 51
3.2.3 製備丙烯酸溶液 53
3.2.4 電漿輔助塗佈 53
3.3 分析方法 54
3.3.1 表面化學元素分析 54
3.3.2 表面結構分析 55
3.3.3 吸收波長分析 56
3.3.4 酚的濃度測定 56
3.3.5 甲基藍的濃度測定 58
3.3.6 紫外光直接降解實驗 58
3.3.7 不同觸媒含量複合膜之降解影響 60
第四章 實驗結果與討論 62
4.1 二氧化鈦/氧化石墨烯複合膜物性分析 62
4.1.1 X-ray繞射分析 62
4.1.2 表面結構分析 71
4.1.3 表面化學元素組成分析 83
4.2 對照組實驗與基本分析 98
4.2.1 降解水溶液性質分析 98
4.2.2 直接光降解實驗 99
4.3 複合膜對紫外光系統降解 101
4.3.1 不同觸媒含量複合膜降解 101
4.3.2 溶膠凝膠法製備複合膜酚降解 125
第五章 結論 132
參考文獻 133

 
圖目錄
圖2.1 二氧化鈦之晶體結構 9
圖2.2 二氧化鈦之分子鍵結方式 10
圖2.3 二氧化鈦電子受激躍遷示意圖 13
圖2.4 光催化反應內部的反應意示圖 13
圖2.5 二氧化鈦光催化反應機制 15
圖2.6 石墨可組成不同型態之材料 18
圖2.7 化學剝離法製備氧化石墨烯 21
圖2.8 石墨烯/二氧化鈦光降解機制 22
圖2.9 二氧化鈦奈米晶對氧化石墨烯片材合成機制 24
圖2.10 陰離子活性劑調節石墨烯/二氧化鈦混合奈米結構 25
圖2.11 酚光降解路徑 29
圖2.12 甲基藍降解路徑 31
圖2.13 薄膜固定化流程圖 36
圖2.14 斷鏈轉移示意圖 38
圖2.15 不同二氧化鈦表面官能基配位 39
圖3.1氣旋式大氣電漿設備示意圖 44
圖3.2氣旋式大氣電漿實體照 44
圖3.3射頻電漿電源供應器 45
圖3.4 氣體流量控制器材 45
圖3.5 塗佈反應器構造及實體圖 46
圖3.6 SEN高壓汞燈光譜放射能量分布 48
圖3.7 SEN高壓汞燈示意圖 48
圖3.8降解實驗反應裝置圖（1） 49
圖3.9降解實驗反應裝置構造圖（2） 50
圖3.10光催化降解實驗裝置圖 50
圖4.1 JCPDS資料庫 64
圖4.2 商業型Degussa P25二氧化鈦XRD分析圖譜 65
圖4.3 溶膠凝膠製備二氧化鈦XRD分析圖譜 65
圖4.4 石墨XRD分析圖譜 68
圖4.5 氧化石墨烯XRD分析圖譜 68
圖4.6 經電漿處理後之複合材XRD分析圖譜 69
圖4.7 未處理PVDF薄膜XRD分析圖譜 69
圖4.8 PVDF-g-PAA-GO複合膜之XRD分析圖譜 70
圖4.9 PVDF-g-PAA-P25 TiO2複合膜之XRD分析圖譜 70
圖4.10 溶膠凝膠法製備二氧化鈦SEM圖 71
圖4.11 商業型Degussa P25二氧化鈦SEM圖 72
圖4.12 PVDF原膜SEM俯視圖 73
圖4.13 PVDF原膜SEM剖面圖 73
圖4.14 PVDF-g-PAA SEM俯視圖 74
圖4.15 PVDF-g-PAA-GO SEM俯視圖 74
圖4.16 PVDF-g-PAA-GO SEM剖面圖 75
圖4.17 PVDF-g-PAA-P25 SEM俯視圖 75
圖4.18 PVDF-g-PAA-P25 SEM剖面圖 76
圖4.19 PVDF-g-PAA-P25/GO SEM俯視圖 76
圖4.20 PVDF-g-PAA-P25/GO SEM剖面圖 77
圖4.21 PVDF-g-PAA-P25 SEM圖 78
圖4.22 PVDF-g-PAA-P25/GO SEM 圖 79
圖4.23 天然石墨TEM 圖 80
圖4.24 氧化石墨烯TEM 圖 80
圖4.25 經電漿處理後氧化石墨烯TEM圖 81
圖4.26 經電漿處理後P25/GO TEM圖 82
圖4.27 經電漿處理後之複合材Raman光譜圖 83
圖4.28丙烯酸於PVDF薄膜與接觸角圖 84
圖4.29 丙烯酸濃度與接觸角關係圖 85
圖4.30大氣電漿輔助塗佈複合膜FTIR-ATR圖 86
圖4.31氧化石墨烯XPS全譜圖 88
圖4.32 複合材XPS碳元素分峰圖 89
圖4.33 PVDF-g-PAA XPS碳元素分峰圖 91
圖4.34 PVDF-g-PAA-GO XPS碳元素分峰圖 92
圖4.35 PVDF-g-PAA-TiO2 XPS碳元素分峰圖 94
圖4.36 PVDF-g-PAA-TiO2/GO XPS碳元素分峰圖 96
圖4.37 XPS鈦元素分峰圖 97
圖4.38 酚溶液UV-Vis吸收光譜圖 98
圖4.39 甲基藍溶液UV-Vis吸收光譜圖 99
圖4.40 酚直接光降解實驗 100
圖4.41甲基藍直接光降解實驗 100
圖4.42 P25複合膜降解酚效率變化 102
圖4.43 P25複合膜降解酚一階反應 103
圖4.44定量比例P25/GO複合膜降解酚效率變化 106
圖4.45定量比例P25/GO複合膜降解酚一階反應 109
圖4.46 不同比例P25/GO複合膜降解酚效率變化 112
圖4.47 不同比例P25/GO複合膜降解酚一階反應 115
圖4.48 P25複合膜效率降解甲基藍變化 117
圖4.49 P25複合膜降解甲基藍一階反應 119
圖4.50定量比例P25/GO複合膜降解甲基藍效率變化 121
圖4.51定量比例P25/GO複合膜降解甲基藍一階反應 124
圖4.52 溶膠凝膠法二氧化鈦複合膜重複利用效率變化 127
圖4.53 溶膠凝膠法二氧化鈦複合膜一階反應 130

 
表目錄
表2.1 銳鈦礦與金紅石晶型之物理特性比較 11
表2.2 石墨烯製備方法 20
表2.3 酚之物理化學性質 28
表2.4 甲基藍之物理化學性質 30
表2.5 丙烯酸之物理化學性質 37
表3.1燈源特性資料表 47
表3.2 HPLC最佳操作條件 57
表4.1各種樣品的臨界波長與能階 67
表4.2 拉曼光譜波峰值比較 82
表4.3丙烯酸於PVDF薄膜與接觸角關係 85
表4.4 複合材元素比例分析 90
表4.5 PVDF-g-PAA複合膜元素比例分析 91
表4.6 PVDF-g-PAA-GO複合膜元素比例分析 93
表4.7 PVDF-g-PAA-TiO2複合膜元素比例分析 94
表4.8 PVDF-g-PAA-GO/TiO2複合膜元素比例分析 96
表4.9 P25複合膜對酚之移除率 102
表4.10 P25複合膜降解速率表 104
表4.11 定量P25/GO複合膜對酚之移除率 107
表4.12 定量P25/GO複合膜降解速率表 110
表4.13 不同比例P25/GO複合膜對酚之移除率 113
表4.14 不同比例P25/GO複合膜降解速率表 116
表4.15 P25複合膜對甲基藍之移除率 118
表4.16 P25複合膜降解甲基藍速率表 119
表4.17 定量P25/GO複合膜對甲基藍之移除率 122
表4.18 定量P25/GO複合膜降解甲基藍速率表 125
表4.19 溶膠凝膠法二氧化鈦複合膜對酚之移除率 128
表4.20 溶膠凝膠法二氧化鈦複合膜降解速率表 131

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