臺灣博碩士論文加值系統

本研究以自製聚氨酯(polyurethane, PU)黏結劑及聚偏氟乙烯(polyvinylidene fluoride, PVDF)黏結劑探討改質之TiO2/AC活性碳電極，使用電容去離子技術(capacitive deionization, CDI)以自組式CDI模型廠進行銦離子吸附。
實驗第一部分結果顯示，以四種不同碳材進行循環伏安法(cyclic voltammetry, CV)及電化學阻抗頻譜(electrochemical impedance spectroscopy, EIS)所測得出石油焦活性碳(AC-p)之CV及EIS皆具備良好之電化學特性，PU及PVDF之活性碳電極電吸附容量可達到122.4 F/g及136.3 F/g，由波德圖(Bode plot)亦顯示出AC-p具有最低電子阻抗並以垂直電容形式上升，可證明PU黏結劑之活性碳電極電容效能與PVDF之活性碳電極效能相近，後續以TiO2作AC-p改質實驗用於銦吸附實驗。
第二部分探討四種不同TiO2改質活性碳之實驗，以(microwave-assisted ionothermal synthesis of titanium, MAIS TiO2)/AC-p所合成之複合碳電極其電吸附容量及EIS電化學特性皆達到良好之電容效能，且由奈式圖(nyquist plot)之結果證明MAIS TiO2/AC-p於低頻阻抗區域電子阻抗最低成垂直電容形式上升，可比擬純碳材活性碳電極。
本研究第三部分以PU及PVDF黏結劑之MAIS TiO2/AC-p複合碳電極進行不同濃度之CDI銦吸附實驗，實驗數據可說明於低濃度下PU之複合碳電極具有良好之吸附效果，高濃度為PVDF效果較佳，且從等溫吸附模式曲線亦說明低濃度適用Langmuir模式，高濃度則適用Freundlich模式，說明PU黏結劑之黏結性能可取代PVDF。

This research is about experimenting self-made polyurethane (PU) binder and polyvinylidene fluoride (PVDF) binder on TiO2 activated carbon electrode by performing Indiun (In^(3+))electrosorption using self-assembled CDI module.
The result obtained from the first part of the experiment indicated that petroleum coke (AC-p) has a higher electrochemical characteristic after performing cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) on four types of activated carbon (AC). The electrosorption capacity of PU- activated carbon electrode and PVDF-activated carbon electrode was able to reach 122.4 F/g and 136.3 F/g. As shown in Bode plot, AC-p has the lowest internal resistance and highest electricity conductivity, proving that the efficiency of PU-activated carbon electrode is closely similar to PVDF-activated carbon electrode. From the analysis, the most appropriate type of electrode materials to be used in CDI application is TiO2/AC-p.
The second part of the experiment explored on four different TiO2/AC. An enhancement in electrosorption capacity and EIS electrochemical characteristic was observed for the TiO2/AC-p prepared by a two-step microwave-assisted ionothermal synthesis (MAIS) method. The result from nyquist plot indicated that MAIS TiO2/AC-p has the smallest diameter of the semi-circle, matching the efficiency of a pure activated carbon electrode.
Next, the third part of the experiment focused on using different concentration of PU and PVDF MAIS TiO2/AC-p to perform CDI Indiun electrosorption. At lower concentration, it is beneficial to use PU activated carbon electrode. On the contrary, at higher concentration, PVDF is more favorable. By using the Langmuir and Freundlich model, the data obtained has shown that the efficiency of PU is closely similar to PVDF which increase the possibility of replacing PVDF with PU.

總目錄
中文摘要 I
ABSTRACT III
致謝 V
總目錄 VII
圖目錄 XI
表目錄 XIV
第一章 前言 1
1.1 研究源起 1
1.2 研究內容及目的 3
第二章 文獻回顧 4
2.1 電容去離子技術基本原理 4
2.1.1 電容吸附之理論及特性 4
2.1.2 電容去離子技術之發展 6
2.2 碳電極材料之組成與應用特性 8
2.2.1碳電極材料之組成 8
2.3 電容去離子技術之黏結劑 17
2.3.1 聚氨酯(PU)黏結劑 17
2.3.2 聚偏氟乙烯(PVDF)黏結劑 19
2.4 銦離子選擇性吸附之原理與特性 21
2.4.1 銦離子之基本性質 21
2.4.2 選擇性吸附之原理與特性 23
2.4.3 光電產業廢水銦法規管制及標準 24
第三章 實驗材料與方法 26
3.1 研究方法 26
3.1.1 研究架構 26
3.2 實驗設備 28
3.2.1 自組式CDI模型廠 28
3.3 實驗材料與分析方法 30
3.3.1 極板製作方法及實驗藥品 30
3.3.2 複合碳電極材料之改質及實驗藥品 35
3.3.3 分析設備與方法 38
第四章 結果與討論 43
4.1 PU及PVDF使用於四種活性碳材之比較 43
4.1.1 AC-w之CV及EIS電吸附容量探討 43
4.1.2 AC-p之CV及EIS電吸附容量探討 50
4.1.3 AC-c之CV及EIS電吸附容量探討 55
4.1.4 AC-b之CV及EIS電吸附容量探討 61
4.1.5 四種活性碳材綜合比較 67
4.2 TiO2/AC-p複合活性碳電極之改質 68
4.2.1 TiO2/AC-p複合電極電吸附容量之比較 68
4.2.2 EIS探討TiO2/AC-p複合電極電吸附容量之比較 70
4.2.3 TiO2/AC-p複合電極綜合性探討 73
4.3 TiO2/AC-p複合電極之CDI銦吸附探討 74
4.3.1 不同濃度之吸附效果 74
4.3.2 吸附特性及模式分析 91
第五章 結論與建議 94
5.1 結論 94
5.2 建議 96
參考文獻 97
附錄 103
附錄1 AC-w/PU表面結構特性SEM圖 103
附錄2 AC-w/PVDF表面結構特性SEM圖 104
附錄3 AC-p/PU表面結構特性SEM圖 105
附錄4 AC-p/PVDF表面結構特性SEM圖 106
附錄5 AC-c/PU表面結構特性SEM圖 107
附錄6 AC-c/PVDF表面結構特性SEM圖 108
附錄7 AC-b/PU表面結構特性SEM圖 109
附錄8 AC-b/PVDF表面結構特性SEM圖 110
附錄9 MAIS TiO2 /AC-p PU表面結構特性SEM圖 111
附錄10 MAIS TiO2 /AC-p PVDF表面結構特性SEM圖 112
附錄11 MAIS TiO2/AC-p及AC-p之XPS特性分析 113

圖目錄
圖2.1 電容去離子技術電吸附原理之說明圖 4
圖2.2 電雙層示意圖 5
圖2.4 孔隙大小定義(IUPAC) 9
圖2.5 加入CB及未加入CB之循環伏安圖 11
圖2.6 改質活性碳於不同NaCl濃度之回收效率 15
圖2.7 添加TiO2及未添加TiO2之CV圖 16
圖2.8 世界近六十年銦金屬產量(公噸) (工業污染防治，2010) 22
圖3.1 研究架構圖 27
圖3.2 電容去離子實驗示意圖 28
圖3.3 CDI實驗流程圖 29
圖3.4 極板製作過程 32
圖3.5 聚氨酯彈性體結構說明 33
圖3.6 MAIS TiO2製備方法 37
圖4.2 AC-w PU及PVDF 奈式圖：(a)AC-w全頻圖、(b) AC-w低頻圖 47
圖4.3 AC-w PU及PVDF 之波德圖 49
圖4.4 AC-w PU及PVDF 之比電容圖 49
圖4.5 AC-p PU及PVDF之CV圖 51
圖4.6 AC-p PU及PVDF 奈式圖：(a)AC-p全頻圖、(b) AC-p低頻圖 52
圖4.7 AC-p PU及PVDF波德圖 54
圖4.8 AC-p PU及PVDF比電容圖 54
圖4.9 AC-c PU及PVDF之CV圖 56
圖4.10 AC-c PU及PVDF 奈式圖：(a)AC-c全頻圖、(b) AC-c低頻圖 58
圖4.11 AC-c PU及PVDF波德圖 60
圖4.12 AC-c PU及PVDF比電容圖 60
圖4.13 AC-b PU及PVDF之CV圖 62
圖4.14 AC-b PU及PVDF 奈式圖：(a)AC-b全頻圖、(b) AC-b低頻圖 64
圖4.15 AC-b PU及PVDF波德圖 66
圖4.16 AC-b PU及PVDF比電容圖 66
圖4.17 TiO2/AC-p PU奈式圖： 71
(a) TiO2/AC-p PU全頻圖、(b) TiO2/AC-p PU低頻圖 71
圖4.18 TiO2/AC-p PU之波德圖 72
圖4.19 TiO2/AC-p PU之比電容圖 73
圖4.20 銦濃度1 mg/L之EC變化圖 76
圖4.21 銦濃度1 mg/L之pH變化圖 76
圖4.22 銦濃度5 mg/L之EC變化圖 78
圖4.23 銦濃度5 mg/L之pH變化圖 78
圖4.24 銦濃度10 mg/L之EC變化圖 80
圖4.25 銦濃度10 mg/L之pH變化圖 80
圖4.26 銦濃度25 mg/L之EC變化圖 82
圖4.27 銦濃度25 mg/L之pH變化圖 82
圖4.28 銦濃度50 mg/L之EC變化圖 84
圖4.29 銦濃度50 mg/L之pH變化圖 84
圖4.30 Blank之 EC圖 86
圖4.31 Blank之pH圖 86
圖4.32 未添加TiO2之銦濃度10 mg/L EC圖 88
圖4.33 未添加TiO2碳電極之銦濃度10 mg/L pH圖 88
圖4.33 PVDF之複合碳電極Langmuir及Freundlich等溫吸附曲線圖 93

表目錄
表2.1 不同電極材料之實用性比較 13
表2.2 於不同NaCl濃度下四種不同碳材之CV電容量 14
表2.3 XPS分析AC碳材之表面特性 16
表2.4 銦基本性質 22
表2.5 不同奈米材料對銦離子吸附之影響 23
表2.6 銦、鎵、鉬管制標準 25
表3.1 自組式CDI模型廠電極材料&基本參數 29
表3.2 極板製作材料及用藥廠牌 30
表3.3 PU黏結劑結構特性 34
表3.4 複合碳電極之改質材料與藥品 35
表3.5 製備MAIS TiO2實驗藥品 37
表3.6 實驗用設備及廠牌型號 41
表3.7 水質項目之分析方法 42
表4.1 AC-w之材料基本性質 44
表4.2 AC-w PU及PVDF之電容特性 45
表4.3 AC-p之材料基本性質 50
表4.4 AC-p PU及PVDF之電容特性 50
表4.5 AC-c之材料基本性質 55
表4.6 AC-c PU及PVDF之電容特性 56
表4.7 AC-b之材料基本性質 61
表4.8 AC-b PU及PVDF之電容特性 62
表4.9 不同In3+濃度之CDI電吸附去除特性 90
表4.10 In3+之等溫吸附曲線之模擬相關參數 92

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