以去官能基化二氧化鈦/單壁奈米碳管複合材料修飾玻璃碳電極進行COD之伏安法分析

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盧怡君(Yi-chun Lu) 查詢紙本館藏

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論文名稱

以去官能基化二氧化鈦/單壁奈米碳管複合材料修飾玻璃碳電極進行COD之伏安法分析
(Using the defunctionalized TiO2/SWCNTs composite modified GCE to analyze COD via voltammetry)

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摘要(中)

化學需氧量(chemical oxygen demand, COD)是用來檢測水中有機污染物含量以及水質監測的重要參數之一。為了減少傳統分析方法所帶來的廢液及有害物，並且減少分析上的誤差，本研究製備去官能基化TiO2/ SWCNTs修飾玻璃碳電極進行COD之伏安法分析。經由表面物化特性以及電流反應強度分析，去官能基後的複合材料表面並不會受到破壞且仍具有催化效果，最後選定以高溫300℃處理的TiO2/ SWCNTs為修飾電極。藉由模擬水樣分析結果顯示，去除TiO2/ SWCNTs表面官能基後，修飾電極確實有較佳的穩定度以及準確度，電流值與COD濃度也有良好的線性關係，並且可量測至0.1 mg/L。在進行多次實場廢水分析結果顯示，對於處理過的或是組成較單純的廢水，LSV法與COD標準方法所得到的變化趨勢相近。

摘要(英)

Chemical oxygen demand (COD) is usually monitored because it is one of the important water qualities, which indicates the degree of pollution by organic compounds. To reduce the error in analysis and to limit the consumption of toxic chemicals in standard COD analysis, GCE electrodes were modified by defunctionalized TiO2/ SWCNTs composite and used in COD measurements via voltammetry. The surface physical and chemical properties of TiO2/ SWCNTs composite have been investigated. It was found that the TiO2/ SWCNTs composite treated at 300℃ has the least amount of functional groups and the best electrical property. It was also found that by defunctionalizaion of TiO2/ SWCNTs has improved the stability and the sensitivity of linear scanning voltammetry (LSV). Good correlation between oxidation peak current and COD concentration of modeled water and a low detection limit to 0.1 mg/L were achieved. The analysis of real wastewater samples was carried out by both the LSV and the standard dichromate method. It is found that COD values determined via LSV and standard dichromate method had similar results when the wastewater was treated.

關鍵字(中)

★ 線性掃描伏安法
★ TiO2/ CNTs
★ 熱處理

關鍵字(英)

★ Linear sweep voltammetry
★ TiO2/ CNTs
★ thermal treatment

論文目次

摘要…………………………………………………………………………………………………………………………………I
Abstract……………………………………………………………………………………………………………………II
誌謝………………………………………………………………………………………………………………………………III
圖目錄…………………………………………………………………………………………………………………………VIII
表目錄…………………………………………………………………………………………………………………………XI
第一章前言……………………………………………………………………………………………………………1
1-1 研究緣起………………………………………………………………………………………………………………1
1-2 研究動機………………………………………………………………………………………………………………3
1-3 研究目的………………………………………………………………………………………………………………3
1-4 研究流程………………………………………………………………………………………………………………4
第二章文獻回顧……………………………………………………………………………………………………5
2-1 COD檢測方法………………………………………………………………………………………………………5
2-2 電化學分析…………………………………………………………………………………………………………8
2-2-1 電化學反應……………………………………………………………………………………………………8
2-2-2 循環伏安法……………………………………………………………………………………………………9
2-2-2 線性掃描伏安法………………………………………………………………………………………10
2-3 奈米碳管……………………………………………………………………………………………………………11
2-3-1 奈米碳管基本特性……………………………………………………………………………………11
2-3-2 奈米碳管的純化與改質…………………………………………………………………………13
2-4 奈米碳管修飾電極電化學分析應用………………………………………………………16
2-4-1奈米碳管修飾電極………………………………………………………………………………………16
2-5 奈米碳管複合材料製備及去官能基處理………………………………………………18
2-5-1 TiO2/CNTs複合材料製備……………………………………………………………………18
2-5-2複合材料表面改質………………………………………………………………………………………19
2-6 奈米碳管修飾電極對電化學訊號的影響………………………………………………22
第三章實驗方法…………………………………………………………………………………………………24
3-1 實驗材料與設備……………………………………………………………………………………………24
3-1-1 實驗材料……………………………………………………………………………………………………24
3-1-2 實驗設備……………………………………………………………………………………………………26
3-2 實驗方法…………………………………………………………………………………………………………29
3-2-1 單壁奈米碳管酸化處理………………………………………………………………………29
3-2-2 製備TiO2/ SWCNTs複合材料…………………………………………………………30
3-2-3 TiO2/ SWCNTs去官能基處理…………………………………………………………31
3-2-4 貝姆滴定法(Boehm’s titration)……………………………………………32
3-2-5 複合材料修飾電極製備………………………………………………………………………32
3-2-6電化學分析…………………………………………………………………………………………………33
第四章結果與討論…………………………………………………………………………………………37
4-1 複合材料之特性鑑定…………………………………………………………………………………37
4-1-1 晶相分析……………………………………………………………………………………………………37
4-1-2 比表面積與孔洞分析……………………………………………………………………………38
4-1-3 表面型態觀察…………………………………………………………………………………………38
4-1-4 官能基分析………………………………………………………………………………………………40
4-2 TiO2/ SWCNTs複合材料修飾電極之電化學特性…………………………42
4-2-1 TiO2/ SWCNTs修飾電極前處理……………………………………………………42
4-2-2電極確效性…………………………………………………………………………………………………45
4-2-3修飾電極反應電流測定…………………………………………………………………………47
4-3 奈米碳管修飾電極分析水中COD…………………………………………………………49
4-3-1模擬水樣掃描條件選定及COD分析…………………………………………………50
4-3-2 實場水樣掃描條件選定及COD分析………………………………………………64
4-4 TiO2/ SWCNTs修飾電極對水質之電化學反應……………………………82
4-4-1 固定電位對KHP與SA之影響……………………………………………………………82
第五章　結論與建議…………………………………………………………………………………………87
5-1 結論…………………………………………………………………………………………………………………87
5-2 建議…………………………………………………………………………………………………………………89
參考文獻…………………………………………………………………………………………………………………90

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指導教授

秦靜如(Ching-ju Chin)

審核日期

2015-7-24

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