摘 要

本研究旨在探討二氧化鈦(TiO2)光觸媒之改質，及其在紫外光/二氧化鈦（UV/TiO2）異相光催化分解(heterogeneous photocatalysis)四氯乙烯(perchloroethylene；PCE)之產物分佈，期能提高四氯乙烯之轉化率及礦化率，並進一步探討其可能之反應路徑。本研究所測試之改質光觸媒包括Ag/TiO2、Au/TiO2、Pt/TiO2、WO3/TiO2及AC/TiO2等5種，其添加比例除活性碳（activied carbon；AC）為TiO2光觸媒含量之10wt﹪外，其餘添加物之添加比例均為TiO2光觸媒之0.5wt%。本實驗測試之操作參數包括相對濕度(R.H.=0~60.0﹪)、氧氣濃度(0~21.0﹪)及停留時間(0.38~0.89秒)。

本研究係將披覆改質之Degussa P-25 anatase TiO2的玻璃珠填充在Pyrex玻璃管中，並以四支10W的近紫外燈管做為光催化反應之光源。研究結果顯示，在測試之反應時間內，四氯乙烯無法直接經由365 nm之近紫外光分解，而必需經由異相光催化反應才能被快速分解，且於光活性測試時亦未發現改質觸媒有毒化之現象。在添加改質光觸媒方面，以WO3/TiO2及AC/TiO2之轉化率及礦化率最佳，Ag/TiO2與未改質之TiO2光觸媒並無顯著差異，而Au/TiO2及Pt/TiO2則較差。研究結果顯示PCE轉化率最高可達99.5%，適度的氧氣有助於PCE的分解，但過多則無顯著的助益。此外，增加反應停留時間對PCE之轉化率有明顯的幫助；而相對濕度的存在對PCE之轉化率則會有顯著的抑制作用。

本研究發現PCE光催化分解之最終產物包括CHCl3、CCl4、C2HCl5、C2Cl6、COCl2、CCl3CClO、Cl2、HCl、CO及CO2等。在高氧氣濃度且沒有水份存在時，主要含Cl產物為Cl2；在高氧氣濃度且有水份存在時，主要含Cl產物為HCl；而在高氧氣濃度且不論有無水份存在，則主要含C產物均為CO2。

ABSTRACT
The purpose of this research was to investigate the modified photocatalyst(TiO2) from the heterogeneous photocatalysis of perchloroethylene(PCE) products distribution by different operating conditions using near UV/TiO2 hope that could enhance the PCE’s conversion and mineralization rate and explore the reaction pathways.The modified photocatalyst of this research was completed with Ag/TiO2、Au/TiO2、Pt/TiO2、WO3/TiO2 and AC/TiO2. The added species except activied carbon was 10 % weight of photocatalyst(TiO2) others the noble metal (sillver、gold and platinum) and tungsten oxide(WO3) were 0.5 % weight of TiO2. Then the experiments were conducted by varying relative humidity(R.H.=0~60 %), oxygen concentration(0~21 %), and retention time(0.38~0.89 sec).

Glass beds coated with modified Degussa P-25 anatase TiO2 were filled in a Pyrex glass reactor. TiO2 was illuminated by four 10 watts ultraviolet(UV) lamps. Results from QA/QC experiments indicated that PCE could not be photodegradated by near UV of wavelength 365 nm. However, It can be decomposed quickly through heterogeneous photocatalysis. And it also find that no modified photocatalyst would be envenomed in photoactivied continuance test. The best PCE conversion and mineralization rate of modified photocatalyst were WO3/TiO2 and AC/TiO2. The modified photocatalyst Ag/TiO2 were the same as TiO2 but Au/TiO2 and Pt/TiO2 were worse to TiO2. The highest converstion rate of PCE could top to 99.5 %； The experiment showed that PCE was decomposed as oxygen concentration and retention time increased. But a higher concentration of oxygen was not efficient on the increase of PCE conversion. The conversion ratio of PCE could be inhibited at higher relative humidities.

The end products observed from UV/TiO2 heterogeneous photocatalytic reactions included CHCl3, CCl4, C2HCl5, C2Cl6, COCl2, CCl3CClO, Cl2, HCl, CO, and CO2. The major chlorinated compound was Cl2 when the photocatalytic reactions proceed at higher oxygen concentration and less humid conditions. As water vapor existed, the major chlorinated compound became HCl. The major product was CO2 during the entire experimental process of heterogeneous photocatalytic reactions.

目 錄
摘要………………………………………………………………... Ⅰ
目錄………………………………………………………………... III
表目錄……………………………………………………………... Ⅷ
圖目錄……………………………………………………………... ⅩⅡ
符號說明…………………………………………………………... ⅩⅩⅠ

第一章 諸論………………………………………………………. 1-1
1-1 研究緣起………………………………………………… 1-1
1-2 研究目的………………………………………………… 1-10

第二章 文獻回顧…………………………………………………. 2-1
2-1 含氯揮發性有機物之特性及影響……………………… 2-1
2-2 光催化反應原理………………………………………… 2-12
2-3 半導體之基本特性……………………………………… 2-20
2-3-1 n-型和p-型半導體………………………………… 2-22
2-3-2 半導體光催化劑之種類…………………………... 2-25
2-3-3 半導體之異相光催化原理與機制………………... 2-30
2-4 光催化觸媒的製備……………………………………… 2-33
2-5 光催化反應器…………………………………………… 2-35
2-6 影響UV/TiO2光催化反應之操作參數…………………. 2-37
2-6-1 濕度的影響………………………………………... 2-37
2-6-2 光強度的影響……………………………………... 2-38
2-6-3 氧濃度的影響……………………………………... 2-39
2-6-4 溫度的影響………………………………………... 2-40
2-7 半導體觸媒的改質……………………………………… 2-41
2-7-1 半導體改質觸媒的製備…………………………... 2-50
2-7-2強金屬載體作用力………………………………… 2-52
2-8 反應途徑的推估………………………………………… 2-55

第三章 研究方法…………………………………………………. 3-1
3-1 實驗設備…………………………………………………. 3-3
3-1-1 VOCs產生系統……………………………………. 3-3
3-1-2光催化反應系統…………………………………… 3-5
3-1-3分析系統…………………………………………… 3-5
3-1-4觸媒還原系統……………………………………… 3-9
3-2 實驗材料及製備方法……………………………………. 3-9
3-2-1實驗材料…………………………………………… 3-9
3-2-2製備方法…………………………………………… 3-13
3-2-2-1 TiO2的製備方法…………………………... 3-14
3-2-2-2 Ag/TiO2觸媒製備方式……………………. 3-14
3-2-2-3 Au/TiO2觸媒製備方式……………………. 3-15
3-2-2-4 Pt/TiO2觸媒製備方式…………………….. 3-16
3-2-2-5 AC/TiO2觸媒製備方式…………………… 3-16
3-2-2-6 WO3/TiO2觸媒製備方式………………….. 3-18
3-3 實驗方法…………………………………………………. 3-18
3-3-1操作參數及範圍……………………………………. 3-18
3-3-2系統特性測試…………………. ………………….. 3-20
3-3-2-1載體吸附和均相光催化反應測試………... 3-20
3-3-2-2不照光吸附反應測試……………………... 3-20
3-3-2-3異相光催化反應測試……………………... 3-20
3-3-2-4光活性持續性測試………………………... 3-21
3-3-3光催化反應實驗……………………………………. 3-21
3-3-4停留時間之計算……………………………………. 3-22
3-4 改質觸媒之物理特性分析………………………………. 3-22
3-5 產物分析方法……………………………………………. 3-23

第四章 結果與討論………………………………………………. 4-1
4-1 光觸媒基本特性分析…………………………………… 4-1
4-1-1外表與顏色觀察結果………………………………. 4-1
4-1-2 X光繞射儀（XRD）分析結果……………………. 4-2
4-1-3掃描式電子顯微鏡（SEM）與能譜儀（EDS）分析結果……………………………………………...
4-3
4-1-4紫外光可見光譜儀（UV/Vis Spectroscopy）分析結果……………………………………………….
4-4
4-1-5微孔隙分析儀（Micropore Analyzer）分析結果… 4-5
4-2 實驗系統特性測試結果………………………………… 4-8
4-2-1載體吸附測試結果…………………………………. 4-9
4-2-2均相光反應測試結果………………………………. 4-9
4-2-3不照光實驗測試結果………………………………. 4-11
4-2-4異相光催化反應實驗測試結果……………………. 4-13
4-2-5光活性持續性測試結果……………………………. 4-15
4-3 光催化反應產物分析結果……………………………… 4-17
4-4 操作條件對改質光觸媒分解PCE效率之探討………... 4-19
4-4-1氧氣濃度對改質光觸媒分解PCE效率之探討……. 4-19
4-4-2停留時間對改質光觸媒分解PCE效率之探討……. 4-24
4-4-3相對濕度對改質光觸媒分解PCE效率之探討……. 4-28
4-5 操作條件對改質光觸媒分解PCE產物及產率之影響... 4-32
4-5-1氧氣濃度對改質光觸媒分解PCE產物及產率之影響………………………………………………...
4-33
4-5-2停留時間對改質光觸媒分解PCE產物及產率之影響………………………………………………...
4-71
4-5-3相對濕度對改質光觸媒分解PCE產物及產率之影響………………………………………………...
4-94
4-6 反應途徑之探討………………………………………… 4-129
4-6-1不同氧氣濃度下光催化反應路徑推估……………. 4-129
4-6-2低相對濕度下光催化反應路徑推估………………. 4-134

第五章 結論與建議………………………………………………. 5-1
5-1 結論……………………………………………………… 5-1
5-2建議………………………………………………………. 5-4

參考文獻…………………………………………………………... 6-1
附錄A PCE之特性……………………………………………….. A-1
附錄B不同觸媒之製備方法優缺點比較………………………... B-1
附錄C TiO2（anatase）XRD之JCPDS card……………………. C-1
附錄D GC/ECD、GC/FID層析圖例…………………………….. D-1





表目錄
表1-1 常用有機溶劑可能導致之危害………………………... 1-2
表1-2 含氯有機溶劑之致癌潛在性一覽表…………………... 1-5
表1-3 美國環境保護署129種優先管制污染物清單………… 1-6
表1-4 國內列管揮發性有機污染物排序清單………………... 1-7
表1-5 各種揮發性有機污染物處理方法之比較……………... 1-9
表1-6 可用光催化法處理之VOCs種類……………………… 1-11
表2-1 含氯有機溶劑之主要物性一覽表……………………... 2-2
表2-2 含氯有機溶劑之主要用途……………………………... 2-3
表2-3 含氯有機溶劑之空氣暴露容許標準…………………... 2-4
表2-4 含氯有機溶劑危害人體健康之器官系統……………... 2-5
表2-5 大氣中常見揮發性有機化合物之種類………………... 2-7
表2-6 室內空氣中典型的有機性溶劑………………………... 2-8
表2-7 揮發性有機物排放標準………………………………... 2-9
表2-8 室內常見之35種揮發性有機物種類與濃度…………. 2-10
表2-9 常見之室內揮發性有機物及其職業暴露限制值……... 2-11
表2-10 化學鍵的斷裂能量……………………………………... 2-13
表2-11 金屬氧化物半導體之分類……………………………... 2-23
表2-12 半導體光觸媒之能量障壁值與激發所須之紫外光波長………………………………………………………...
2-26
表2-13 不同溫度下以烴氧化物製備TiO2的特性……………... 2-29
表2-14 TiO2鍛燒溫度與孔隙度和比表面積之關係…………... 2-29
表2-15 光觸媒改質文獻整理…………………………………... 2-42
表2-16 ⅧB金屬觸媒對乙烯(ethane)氫解反應的催化活性…... 2-53
表3-1 球狀活性碳之基本物理性質…………………………... 3-17
表3-2 觸媒製備之配比………………………………………... 3-19
表3-3 操作參數及範圍…………………………………... 3-18
表3-4 GC/ECD分析含氯產物之滯留時間…………………… 3-24
表3-5 CO2之滯留時間………………………………………… 3-25
表3-6 氯化氫分析相關品管數據……………………………... 3-27
表3-7 各分析項目之減量線…………………………………... 3-32
表4-1 添加改質改質光觸媒之物理性質比較表……………... 4-6
表4-2 各改質觸媒異相光催化結果…………………………... 4-14
表4-3 以UV/TiO2程序處理氣相空氣污染物相關研究文獻整理……………………………………………………...
4-18
表4-4 不同觸媒對於光分解PCE產物之比較……………….. 4-70
表4-5 不同觸媒對於光分解PCE產物之比較……………….. 4-93
表4-6 不同觸媒對於光分解PCE產物之比較……………….. 4-128
表A-1 PCE之特性……………………………………………... A-1
表A-2 TiO2的基本性質及應用………………………………... A-2
表A-3 TiO2之基本物理化學特性…………………………….. A-3
表A-4 P-25 TiO2之物理化學特性……………………………. A-3
表B-1 不同觸媒製備方法之優點比較………………………... B-1
表B-2 泥漿反應器之優缺點…………………………………... B-2
表B-3 薄膜反應器之優缺點…………………………………... B-2
表B-4 填充床反應器之優缺點……………………………….. B-3
表B-5 光纖反應器之優點……………………………………... B-3
表B-6 流體化床反應器之優缺點……………………………... B-4
表B-7 UV/TiO2光催化反應中光強度的影響………………… B-5
表B-8 UV/TiO2光催化反應中濕度的影響…………………… B-6
表B-9 UV/TiO2光催化反應中溫度的影響…………………… B-7
表B-10 UV/TiO2光催化反應中氧濃度的影響………………… B-7
表B-11 觸媒製造程序之分類…………………………………... B-8
表C-1 TiO2（anatase）XRD 之JCPDS card………………… C-1
表C-2 TiO2（rutile）XRD 之JCPDS card…………………….. C-1
表C-3 Ag XRD 之JCPDS card………………………………... C-2
表C-4 Au XRD 之JCPDS card………………………………. C-2
表C-5 Pt XRD 之JCPDS card………………………………… C-3
表C-6 WO3 XRD 之JCPDS card……………………………… C-3
表D-1 不同觸媒在不同氧氣濃度下之光催化反應結果一覽表………………………………………………………..
D-9
表D-2 不同觸媒在不同相對濕度下之光催化反應結果一覽表………………………………………………………..
D-11
表D-3 不同觸媒在不同停留時間下之光催化反應結果一覽表………………………………………………………...
D-12














圖目錄
圖1-1 各種處理VOCs方法之年成本比較………………….. 1-12
圖2-1 半導體受光激發後之電子-電洞生成及介面反應示意圖 2-15
圖2-2 三種固體之能帶圖………………………………………. 2-21
圖2-3 電子與電洞能量之關係圖………………………………. 2-21
圖2-4 電子轉移圖………………………………………………. 2-32
圖3-1 本研究實驗流程圖………………………………………. 3-2
圖3-2 反應氣體鋼瓶配置圖……………………………………. 3-4
圖3-3 光催化反應示意圖………………………………………. 3-6
圖3-4 反應系統流程圖…………………………………………. 3-7
圖3-5 還原反應設備圖…………………………………………. 3-10
圖4-1 載體吸附及均相光解反應測試結果……………………. 4-10
圖4-2 不照光實驗PCE被各觸媒吸附現象…………………… 4-12
圖4-3 各改質觸媒光活性持續性測試結果……………………. 4-16
圖4-4 各觸媒隨氧氣濃度分解PCE之效率比較……………… 4-20
圖4-5 各觸媒隨停留時間分解P CE之效率比較……………… 4-25
圖4-6 各觸媒隨相對濕度分解PCE之效率比較……………… 4-30
圖4-7 TiO2光分解PCE含氯產物隨氧氣濃度變化趨勢圖…… 4-33
圖4-8 TiO2光分解PCE中含Cl質量百分比隨氧氣濃度變化趨勢圖…………………………………………………….
4-38
圖4-9 TiO2光分解PCE產物中CO及CO2隨氧氣濃度變化趨勢圖…………………………………………………….
4-39
圖4-10 TiO2光分解PCE中含C質量百分比隨氧氣濃度變化趨勢圖…………………………………………………….
4-41
圖4-11 WO3/TiO2光分解PCE含氯產物隨氧氣濃度變化趨勢圖………………………………………………………….
4-42
圖4-12 WO3/TiO2光分解PCE產物中CO及CO2隨氧氣濃度變化趨勢圖……………………………………………….
4-44
圖4-13 WO3/TiO2光分解PCE中含C質量百分比隨氧氣濃度變化趨勢圖……………………………………………….
4-46
圖4-14 WO3/TiO2光分解PCE中含Cl質量百分比隨氧氣濃度變化趨勢圖……………………………………………….
4-47
圖4-15 AC/TiO2光分解PCE含氯產物隨氧氣濃度變化趨勢圖 4-48
圖4-16 AC/TiO2光分解PCE產物中CO及CO2隨氧氣濃度變化趨勢圖………………………………………………….
4-49
圖4-17 AC/TiO2光分解PCE中含C質量百分比隨氧氣濃度變化趨勢圖………………………………………………….
4-52
圖4-18 AC/TiO2光分解PCE中含Cl質量百分比隨氧氣濃度變化趨勢圖……………………………………………….
4-53
圖4-19 Ag/TiO2光分解PCE含氯產物隨氧氣濃度變化趨勢圖 4-54
圖4-20 Ag/TiO2光分解PCE產物中CO及CO2隨氧氣濃度變化趨勢圖………………………………………………….
4-55
圖4-21 Ag/TiO2光分解PCE中含C質量百分比隨氧氣濃度變化趨勢圖………………………………………………….
4-57
圖4-22 Ag/TiO2光分解PCE中含Cl質量百分比隨氧氣濃度變化趨勢圖………………………………………………….
4-58
圖4-23 Au/TiO2光分解PCE含氯產物隨氧氣濃度變化趨勢圖.. 4-59
圖4-24 Pt/TiO2光分解PCE含氯產物隨氧氣濃度變化趨勢圖.. 4-60
圖4-25 Au/TiO2光分解PCE產物中CO及CO2隨氧氣濃度變化趨勢圖………………………………………………….
4-62
圖4-26 Pt/TiO2光分解PCE產物中CO及CO2隨氧氣濃度變化趨勢圖………………………………………………….
4-63
圖4-27 Pt/TiO2光分解PCE中含C質量百分比隨氧氣濃度變化趨勢圖………………………………………………….
4-64
圖4-28 Pt/TiO2光分解PCE中含Cl質量百分比隨氧氣濃度變化趨勢圖………………………………………………….
4-65
圖4-29 Au/TiO2光分解PCE中含C質量百分比隨氧氣濃度變化趨勢圖………………………………………………….
4-66
圖4-30 Au/TiO2光分解PCE中含Cl質量百分比隨氧氣濃度變化趨勢圖………………………………………………….
4-67
圖4-31 各觸媒光分解PCE產物之產率隨氧氣濃度變化趨勢圖 4-69
圖4-32 TiO2光分解PCE含氯產物隨停留時間變化趨勢圖…… 4-72
圖4-33 TiO2光分解PCE中含Cl質量百分比隨停留時間變化趨勢圖…………………………………………………….
4-74
圖4-34 TiO2光分解PCE產物中CO及CO2隨停留時間變化趨勢圖…………………………………………………….
4-75
圖4-35 TiO2光分解PCE中含C質量百分比隨停留時間變化趨勢圖…………………………………………………….
4-77
圖4-36 AC/TiO2光分解PCE含氯產物隨停留時間變化趨勢圖 4-78
圖4-37 AC/TiO2光分解PCE產物中CO及CO2隨停留時間變化趨勢圖………………………………………………….
4-80
圖4-38 AC/TiO2光分解PCE中含C質量百分比隨停留時間變化趨勢圖………………………………………………….
4-81
圖4-39 AC/TiO2光分解PCE中含Cl質量百分比隨停留時間變化趨勢圖……………………………………………….
4-82
圖4-40 WO3/TiO2光分解PCE含氯產物隨停留時間變化趨勢圖………………………………………………………….
4-83
圖4-41 WO3/TiO2光分解PCE產物中CO及CO2隨停留時間變化趨勢圖……………………………………………….
4-84
圖4-43 WO3/TiO2光分解PCE中含C質量百分比隨停留時間變化趨勢圖……………………………………………….
4-86
圖4-43 WO3/TiO2光分解PCE中含Cl質量百分比隨停留時間變化趨勢圖……………………………………………….
4-87
圖4-44 Ag/TiO2光分解PCE含氯產物隨停留時間變化趨勢圖. 4-88
圖4-45 Ag/TiO2光分解PCE產物中CO及CO2隨停留時間變化趨勢圖………………………………………………….
4-89
圖4-46 Ag/TiO2光分解PCE中含C質量百分比隨停留時間變化趨勢圖…………………………………………………. 4-90
圖4-47 Ag/TiO2光分解PCE中含Cl質量百分比隨停留時間變化趨勢圖………………………………………………….
4-91
圖4-48 各觸媒光分解PCE產物之產率隨停留時間變化趨勢圖 4-92
圖4-49 TiO2光分解PCE產物中含氯產物隨濕度變化趨勢圖… 4-95
圖4-50 TiO2光分解PCE中含Cl質量百分比隨濕度變化趨勢圖………………………………………………………….
4-98
圖4-51 TiO2光分解PCE產物中CO及CO2隨濕度變化趨勢圖………………………………………………………….
4-99
圖4-52 TiO2光分解PCE產物中含C質量百分比隨濕度變化趨勢圖…………………………………………………….
4-101
圖4-53 AC/TiO2光分解PCE產物中含氯產物隨濕度變化趨勢圖………………………………………………………….
4-102
圖4-54 AC/TiO2光分解PCE中含Cl質量百分比隨濕度變化趨勢圖…………………………………………………….
4-104
圖4-55 AC/TiO2光分解PCE產物中CO及CO2隨濕度變化趨勢圖……………………………………………………….
4-105
圖4-56 AC/TiO2光分解PCE產物中含C質量百分比隨濕度變化趨勢圖………………………………………………….
4-106
圖4-57 WO3/TiO2光分解PCE產物中含氯產物隨濕度變化趨勢圖……………………………………………………….
4-108
圖4-58 WO3/TiO2光分解PCE產物中CO及CO2隨濕度變化趨勢圖…………………………………………………….
4-109
圖4-59 WO3/TiO2光分解PCE中含Cl質量百分比隨濕度變化趨勢圖…………………………………………………….
4-110
圖4-60 WO3/TiO2光分解PCE產物中含C質量百分比隨濕度變化趨勢圖………………………………………………
4-111
圖4-61 Ag/TiO2光分解PCE產物中含氯產物隨濕度變化趨勢圖………………………………………………………….
4-112
圖4-62 Ag/TiO2光分解PCE產物中CO及CO2隨濕度變化趨勢圖……………………………………………………….
4-113
圖4-63 Ag/TiO2光分解PCE中含Cl質量百分比隨濕度變化趨勢圖……………………………………………………….
4-115
圖4-64 Ag/TiO2光分解PCE產物中含C質量百分比隨濕度變化趨勢圖………………………………………………….
4-116
圖4-65 Au/TiO2光分解PCE產物中含氯產物隨濕度變化趨勢圖………………………………………………………….
4-117
圖4-66 Pt/TiO2光分解PCE產物中含氯產物隨濕度變化趨勢圖………………………………………………………….
4-118
圖4-67 Au/TiO2光分解PCE產物中CO及CO2隨濕度變化趨勢圖……………………………………………………….
4-120
圖4-68 Pt/TiO2光分解PCE產物中CO及CO2隨濕度變化趨勢圖……………………………………………………….
4-121
圖4-69 Au/TiO2光分解PCE中含Cl質量百分比隨濕度變化趨勢圖……………………………………………………….
4-122
圖4-70 Pt/TiO2光分解PCE中含Cl質量百分比隨濕度變化趨勢圖……………………………………………………….
4-123
圖4-71 Au/TiO2光分解PCE中含C質量百分比隨濕度變化趨勢圖……………………………………………………….
4-124
圖4-72 Pt/TiO2光分解PCE中含C質量百分比隨濕度變化趨勢圖……………………………………………………….
4-125
圖4-73 各觸媒光分解PCE產物之產率隨相對濕度變化趨勢圖 4-126
圖4-74 PCE光催化之可能反應路徑……………………………. 4-130
圖4-75 PCE光催化之可能反應路徑……………………………. 4-131
圖4-76 PCE光催化之可能反應路徑……………………………. 4-132
圖B-1 各觸媒之能階圖…………………………………………. B-9
圖C-1 TiO2之XRD圖譜………………………………………… C-4
圖C-2 Ag/TiO2之XRD圖譜……………………………………. C-4
圖C-3 Pt/TiO2之XRD圖譜……………………………………. C-5
圖C-4 Au/TiO2之XRD圖譜……………………………………. C-5
圖C-5 WO3/TiO2之XRD圖譜………………………………….. C-6
圖C-6 AC/TiO2之XRD圖譜……………………………………. C-6
圖C-7 TiO2 SEM 照片………………………………………….. C-7
圖C-8 AC/TiO2 SEM 照片……………………………………… C-7
圖C-9 WO3/TiO2SEM 照片…………………………………….. C-7
圖C-10 Pt/TiO2 SEM 照片……………………………………….. C-7
圖C-11 Ag/TiO2 SEM 照片……………………………………… C-7
圖C-12 Au/ TiO2 SEM 照片……………………………………... C-7
圖C-13 EDS之TiO2訊號譜圖……………………………………. C-8
圖C-14 EDS之AC/TiO2訊號譜圖……………………………… C-8
圖C-15 EDS之WO3TiO2訊號譜圖……………………………… C-8
圖C-16 EDS之Pt/TiO2訊號譜圖………………………………… C-9
圖C-17 EDS之Au/TiO2訊號譜圖……………………………… C-9
圖C-18 EDS之Ag/TiO2訊號譜圖……………………………… C-9
圖C-19 添加改質TiO2觸媒其光吸收度變化趨勢圖…………… C-10
圖D-1 GC/ECD層析譜圖……………………………………….. D-1
圖D-2 GC/FID附有甲烷轉化器層析譜圖……………………... D-1
圖D-3 N2質量流量計之流量校正曲線圖………………………. D-2
圖D-4 O2 質量流量計之流量校正曲線圖……………………… D-2
圖D-5 VOC質量流量計之流量校正曲線圖…………………… D-2
圖D-6 C2Cl4之檢量線圖………………………………………… D-3
圖D-7 C2Cl6之檢量線圖………………………………………… D-4
圖D-8 COCl2之檢量線圖………………………………………. D-4
圖D-9 C2HCl5之檢量線圖……………………………………… D-5
圖D-10 HCl之檢量線圖………………………………………….. D-5
圖D-11 CCl4之檢量線圖…………………………………………. D-6
圖D-12 CHCl3之檢量線圖……………………………………….. D-7
圖D-13 氯氣之檢量線圖…………………………………………. D-8
圖D-14 CO2之檢量線圖………………………………………….. D-8
圖D-15 CO之檢量線圖………………………………………….. D-8













符號說明

k:反應速率常數
A:頻率因子( frequency factor)
E:反應活化能( activation energy)
T:絕對溫度(。K)
t：反應停留時間(sec)
V：反應器中填充披覆TiO2玻璃珠之體積(cm3)
V

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