臺灣博碩士論文加值系統

化學需氧量(COD)是檢測水中有機污染負荷的重要的指標。傳統的化學檢測方法除了花費長時間的迴流氧化(約2~4個小時)，還需具毒性、腐蝕性之化學品(如：重鉻酸鉀、硫酸銀等)，可能造成環境二次污染。同時，傳統的化學方法會受到氯離子的干擾且適用的COD範圍窄(約10~220 mg/L)。本研究利用二次陽極氧化法製備出高規則的二氧化鈦奈米管陣列薄膜，將其作為光電催化實驗之電極；並且利用二氧化鈦奈米顆粒及鉑金屬修飾二氧化鈦奈米管陣列，提升材料表面積與活性點。再將上述之TiNT-array系列電極材料經由高溫結晶後和白金片組成一雙極光電催化系統針對不同的有機物做相關性建立，實驗的結果指出以本研究之光電催化系統可量測範圍為0 ~ 500 mg/L；十次重複測量之RSD皆小於5%；偵測極限為1.04 mg/L；長時間材料穩定性之偏差值是± 0.98 mg/L；再採取之實際水樣實驗中，水樣經去氯處理所測得之COD為500 mg/L，但直接以公告方法測量之COD值為251mg/L，低估了約50%，而本研究之方法所測得之COD是445 mg/L，較公告方法準確且不受氯離子干擾。故我們建立出一套快速、準確且無二次污染之COD檢測系統。

Chemical oxygen demand (COD) is an important index for the detection of organic pollutant in water. Traditional chemical detection method needs to reflux a long time under oxidation (about 2 to 4 hours), and toxic, corrosive chemicals (ex. potassium dichromate, silver sulfate, etc.). It may cause secondary pollution in the environment. In addition, Cl- may interference COD detection. Furthermore, the detection range of COD is very norrow and about 10 ~ 220 mg/L with traditional chemical method. In this study, high ordered titanium dioxide nanotube array films were prepared by anodic oxidation. It can work as electrode for the photoelectrocatalytic system. The titanium dioxide nanoparticles and platinum nanoparticles modified titania nanotube arrays were used to enhance the surface area and active of materials. The series of TiNT-array with Platinum were used to make up a photoelectrocatalytic system. The results of experimental show the suitable measuring range is 0 ~ 500 mg/L. Furthermore, the RSD of ten repetition is under 5 % and the detection limit is 1.04 mg/L. The stability of standard deviation is ± 0.98 mg/L. The unknown sample without Cl- is 500 mg/L, but the COD is only 251 mg/L with traditional chemical detection method. when the COD underestimate about 50 %. The COD is 445 mg/L with the photoelectrocatalytic system. It is more accurate and can not be interfered as Cl-. Therefore, the COD detection system was develop fast, accurate, and no secondary pollution.

中文摘要 I
Abstract II
第一章 緒論 1
1.1 研究背景 1
1.2 研究目的與內容 4
第二章 文獻回顧 5
2.1 水中化學需氧量 5
2.2 化學需氧量傳統檢測方法 6
2.2.1 重鉻酸鉀迴流法 6
2.2.2 高錳酸鉀法 6
2.3 傳統檢測方法改良 7
2.3.1 微波加熱取代加熱板 7
2.3.2 光譜分析取代滴定 8
2.4 新型檢測方法 8
2.4.1 臭氧氧化法 8
2.4.2電化學法 9
2.4.3光催化法 10
2.4.4光電催化法 12
2.5 一維結構之二氧化鈦奈米管 14
2.6 陽極氧化法 15
2.7 TiO2奈米管陣列應用於光電化學分析 18
第三章 實驗設備與方法 21
3.1實驗藥品與設備 21
3.1.1實驗藥品 21
3.1.2實驗設備 23
3.2複合型態二氧化鈦奈米管陣列薄膜電極製備 24
3.2.1陽極氧化法(Anodization)製備二氧化鈦奈米管陣列薄膜 24
3.2.2二次陽極氧化修飾二氧化鈦奈米管陣列薄膜 24
3.2.3利用真空蒸鍍法將白金鍍於二氧化鈦奈米管陣列薄膜 25
3.2.4 以SILAR法將TiO2顆粒鍍於m-TiNT-array 26
3.3 二氧化鈦奈米顆粒薄膜電極製備 26
3.3.1 二氧化鈦溶膠凝膠之製備 26
3.3.2 利用刮刀成膜法製備TiNP薄膜 27
3.4 樣品特性分析與方法 27
3.4.1 X光粉末繞射儀 (PXRD) 27
3.4.2掃描式電子顯微鏡(FE- SEM) / X光能譜量散佈分析儀 (EDS) 28
3.4.3高解析穿透式電子顯微鏡(HR-TEM) 29
3.5 環保署公告COD檢測方法─密閉迴流滴定法 30
3.5.1 溶液配置 30
3.5.2方法步驟 31
3.5.3 適用範圍 31
3.6 COD標準液與電解液配置 32
3.6.1 COD標準液配置 32
3.6.2 電解液配置 33
3.7 光電催化法量測水中化學需氧量 34
3.7.1光電催化系統 34
3.7.2 連續循環伏安法(Continuous cyclic voltammograms , CVs) 34
3.7.3 光電流分析實驗 35
第四章 結果與討論 37
4.1 二氧化鈦奈米顆粒薄膜 37
4.1.1 場發射掃描電子顯微鏡影像(FESEM) 37
4.1.2 X光粉末繞射儀鑑定(XRD) 37
4.2 二氧化鈦奈米管陣列薄膜 38
4.2.1 場發射掃描電子顯微鏡影像(FESEM) 38
4.2.2 X光粉末繞射儀鑑定(XRD) 40
4.3 表面修飾後之二氧化鈦奈米管陣列薄膜 41
4.3.1 場發射掃描電子顯微鏡影像(FESEM) 41
4.3.2 場發射穿透式電子顯微鏡(FETEM) 44
4.3.3 X光粉末繞射儀鑑定(XRD) 44
4.4 二氧化鈦奈米顆粒修飾m-TiNT-array 46
4.4.1 場發射穿透式電子顯微鏡(FETEM) 46
4.4.2 X光粉末繞射儀鑑定(XRD) 46
4.5 鉑奈米顆粒修飾m-TiNT-array 47
4.5.1 場發射穿透式電子顯微鏡(FETEM) 47
4.5.2 能量散佈儀(Energy Dispersive System ,EDS) 49
4.5.3 X光粉末繞射儀鑑定(XRD) 50
4.6 光電催化分析之最佳實驗參數 51
4.6.1 紫外光(UV)光強度 51
4.6.2 電解質 53
4.6.3 電解液濃度 57
4.6.4 酸鹼值(pH) 61
4.6.5 電壓 62
4.6.6 溶氧的影響 64
4.7 光電催化分析 65
4.7.1 連續循環伏安 65
4.7.2 修飾後材料比較 66
4.7.3 不同電極材料之穩定性 68
4.7.4 不同電極材料之重複性 70
4.7.5 不同電極材料量測之電流與COD值相關性 73
4.7.6 水中氯離子干擾分析 83
4.7.7 實際盲樣測量之準確性 86
第五章 結論與建議 91
5.1 結論 91
5.2 建議 94
參考文獻 95

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徐貴新著，水質分析實驗，六版修訂，高立圖書，中華民國94年。
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