本研究利用兩種不同電解液製備之二氧化鈦奈米管膜，以及鈦板直接煅燒氧化的二氧化鈦膜，以光電催化進行染料去除效率之影響研究；以及相關的電化學量測，包括開路電壓，閉路電流，交流阻抗，並且找出各系統之最佳煅燒溫度。接著以不同染料，不同外加偏壓進行探討，本研究結果顯示，晶相的變化對於降解率之影響比管長、管徑大。最佳的光電催化材料為以甘油電解液製備，並以600 ℃煅燒者；最佳的光電催化參數為外加偏壓1V。無論電解液為乙二醇或甘油，在600 ℃皆以銳鈦礦與金紅石相混晶存在。比較光催化與光電催化反應速率，光電催化之反應速率遠高於光催化反應。另外發現了，鈦板不須經由陽極氧化，在400 ℃時直接熱氧化，也可獲得不錯之降解率。比較兩種染料的光電催化反應，在相同時間內，亞甲基藍降解率只有甲基橙之一半。

Three types of TiO2 membrane were prepared in this study. Two types of TiO2 nanotube arrays membranes were prepared by two different electrolytes and calcined at different temperatures. The third type of TiO2 membrane was prepared by direct oxidation at different temperatures. The photoelectrocatalytic degradation of dyes in solution phase using the three types of TiO2 membrane calcined at different temperatures and with various bias voltages was performed. Electrochemical analysis including open circuit voltage, short circuit and electrochemical impedance spectroscopy were also performed. The results showed that photoelectrocatalytic reaction efficiency was moderated by types of crystal phase. The best photoelectrocatalytic reaction parameters are electrolyte solution of glycerol, calcination temperature of 600 ℃, and bias voltage of 1V. Either ethylene glycol or glycerol as the electrolyte, anatase and rutile mixed crystal phase exists in the form of TiO2 at 600 ℃. The study also showed that TiO2 prepared by direct thermal oxidation at 400 ℃ performed comparable reaction efficiency, photoelectrocatalytic reaction rates were faster than photocatalytic reaction rates, and photoelectrocatalytic degradation ratios of methylene blue only half of that of methyl orange.

總目錄
摘要 I
Abstract II
總目錄 IV
表目錄 VII
圖目錄 VIII
第一章 前言 1
第二章 文獻回顧 3
2.1二氧化鈦晶體結構與特性 3
2.2煅燒溫度對二氧化鈦奈米管陣列之影響 6
2.3陽極氧化法 8
2.4二氧化鈦奈米管陣列膜製備 10
2.5奈米管的生長機制 12
2.6光催化與光電催化 14
2.7光催化之光電效應 22
2.8 TIO2電極平帶電位 26
2.9交流阻抗譜之應用 29
第三章 材料與方法 32
3.1二氧化鈦電極製備 37
3.1.1二氧化鈦奈米管膜之製備 37
3.1.2二氧化鈦直接熱氧化膜之製備 38
3.2光觸媒電極之特性分析 39
3.2.1 FESEM場發掃描式電子顯微鏡 39
3.2.2X光繞射儀(X-ray Diffactomer) 40
3.2.3電化學量測 41
3.3光電催化反應系統 42
第四章 結果與討論 44
4.1煅燒溫度對二氧化鈦表面型態之影響 44
4.1.1甘油電解液 44
4.1.2乙二醇電解液 48
4.1.3鈦板直接熱氧化 51
4.2陽極氧化過程 52
4.3煅燒溫度對二氧化鈦晶相變化之影響 54
4.3.1甘油電解液 54
4.3.2乙二醇電解液 56
4.3.3鈦板直接熱氧化 58
4.4煅燒溫度對二氧化鈦閉路電流(SCC)之影響 59
4.4.1甘油電解液 59
4.4.2乙二醇電解液 61
4.4.3鈦板直接熱氧化 63
4.5煅燒溫度對二氧化鈦開路電壓(OCV)之影響 66
4.5.1甘油電解液與乙二醇電解液 66
4.5.2鈦板直接熱氧化 70
4.6光催化與光電催化 73
4.7煅燒溫度對二氧化鈦光電催化反應之影響 75
4.7.1甘油電解液 75
4.7.2乙二醇電解液 78
4.7.3鈦板直接熱氧化 81
4.8外加偏壓對光電催化之影響 85
4.9光電催化不同染料之影響 91
4.10照光與未照光之交流阻抗(EIS) 92
4.11不同電極之交流阻抗(EIS) 94
第五章 結論 95
第六章 建議 96
參考文獻 97

表目錄
表2.1不同二氧化鈦晶型的物化特性比較表 6
表2.2光電催化程序的相關文獻整理 20
表3.1實驗儀器設備 34
表3.2實驗材料 35
表3.3實驗藥劑 36


圖目錄
圖2.1二氧化鈦三種主要的晶相結構 5
圖2.2陽極氧化製備奈米管的結構成長示意圖 11
圖2.3二氧化鈦催化反應機制圖 14
圖2.4 液相光伏特電池示意圖 17
圖2.5在受光及外加端壓下電子-電洞在TiO2/電極行徑圖 22
圖2.6 n型半導體與溶液物種接觸前後能帶分佈的情形 24
圖3.1實驗流程 32
圖3.2 TiO2奈米管陣列膜製備流程 33
圖3.3陽極氧化裝置 39
圖3.4光電催化反應裝置 41
圖4.1不同煅燒溫度下奈米管膜之FESEM俯視圖(甘油電解液) 46
圖4.2不同煅燒溫度下奈米管膜形態之FESEM側視圖(甘油電解液) 47
圖4.3不同煅燒溫度下奈米管膜之FESEM俯視圖(乙二醇電解液) 49
圖4.4不同煅燒溫度下奈米管膜形態之SEM側視圖(乙二醇電解液) 50
圖4.5不同煅燒溫度之鈦板直接熱氧化膜FESEM俯視圖 51
圖4.6陽極氧化電流趨勢 53
圖4.7甘油電解液製備二氧化鈦經不同煅燒溫度之XRD圖譜 56
圖4.8乙二醇電解液製備二氧化鈦經不同煅燒溫度之XRD圖譜 57
圖4.9鈦板經不同煅燒溫度直接熱氧化之XRD圖譜 59
圖4.10製備二氧化鈦經不同煅燒溫度之短路光電流(甘油電解液) 61
圖4.11製備二氧化鈦經不同煅燒溫度之短路光電流(乙二醇電解液) 63
圖4.12鈦板經不同煅燒溫度直接熱氧化之短路光電流 65
圖4.13不同煅燒溫度之短路光電流比較 66
圖4.14製備二氧化鈦經不同煅燒溫度之開路光電壓(甘油電解液) 67
圖4.15製備二氧化鈦經不同煅燒溫度之開路光電壓比較(甘油電解液) 68
圖4.16製備二氧化鈦經不同煅燒溫度之開路光電壓(乙二醇電解液) 69
圖4.17製備二氧化鈦經不同煅燒溫度之開路光電壓比較(乙二醇電解液) 70
圖4.18鈦板經不同煅燒溫度直接熱氧化之開路光電壓 71
圖4.19鈦板經不同煅燒溫度直接熱氧化之開路光電壓 72
圖4.20光催化與光電催化降解率之比較 74
圖4.21煅燒溫度對甲基橙溶液光電催化降解率之效應(甘油電解液) 76
圖4.22煅燒溫度對甲基橙溶液光電催化反應速率常數之效應 (甘油電解液) 77
圖4.23煅燒溫度對甲基橙溶液光電催化降解率之效應(乙二醇電解液) 79
圖4.24煅燒溫度對甲基橙溶液光電催化反應速率常數之效應(乙二醇電解液) 80
圖4.25煅燒溫度對甲基橙溶液光電催化降解率之效應(鈦板直接熱氧化) 82
圖4.26煅燒溫度對甲基橙溶液光電催化反應速率常數之效應
(鈦板直接熱氧化) 83
圖4.27不同煅燒溫度之反應速率常數比較 84
圖4.28不同外加偏壓對甲基橙溶液光電催化反應速率常數與反應光電流 (甘油電解液) 86
圖4.29不同外加偏壓對甲基橙溶液光電催化反應速率常數與反應光電流 (乙二醇電解液) 87
圖4.30不同外加偏壓對甲基橙溶液光電催化反應速率常數與反應光電流 (鈦板直接熱氧化) 88
圖4.31不同外加偏壓之反應速率常數比較 89
圖4.32不同外加偏壓之對應光電流比較 90
圖4.33不同二氧化鈦電極對不同染料光電催化反應速率常數之效應
(Ti 400 ℃，G 600 ℃，EG 600 ℃) 91
圖4.34照光與未照光之EIS 93
圖4.35不同二氧化鈦電極之EIS 94

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