臺灣博碩士論文加值系統

本研究是以高壓水熱法(hydrothermal methods)合成矽酸鉍及矽酸鉍複合石墨化氮化碳(graphitic carbon nitride, g-C3N4)，而矽酸鉍複合石墨化氮化碳此新穎的異質結合更是首次以水熱法製造出來。其中g-C3N4是以三聚氰胺在馬弗爐(Muffle Furnace)內鍛燒540℃合成，矽酸鉍以硝酸鉍及矽酸鈉為起始物溶解在1M硝酸水溶液並調整pH值，然後將該水溶液轉移到15毫升高壓釜中以150℃加熱8小時。矽酸鉍複合石墨化氮化碳則是將矽酸鉍和g-C3N4依不同比率混合在高壓釜中以150℃加熱4小時。觸媒樣品以X射線粉末繞射圖(XRD)、場發掃描式電子顯微鏡(FE-SEM )、場發穿透式電子顯微鏡(FE-TEM)、X射線光電子能譜圖(XPS )、光激發螢光光譜(PL)、紫外光-可見光漫反射光譜(DRS)、氮氣吸脫附曲線圖及比表面積測定(BET)、傅立葉轉換紅外線光譜(FT -IR)、電子順磁共振圖譜（EPR）等儀器分析產物的組成，並探討矽酸鉍及矽酸鉍複合g-C3N4對於光催化效率的影響。觸媒的光催化效率是利用光催化反應降解有機汙染物-結晶紫（CV），測量結晶紫（CV）的濃度。

In this study, a series of the bismuth silicate and bismuth silicate composite graphitic carbon nitride (g-C3N4) are prepared using autoclave hydrothermal methods. The novel heterojunctions of BixSiOy/g-C3N4 is fabricated by the hydrothermal method for the first time, in which g-C3N4 is synthesized by calcinations at 540℃ in muffle furnace. Bismuth silicate is prepared by Bi(NO3)3 and Na2SiO3, dissolved in an 1M HNO3 aqueous solution and adjusted the pH value, and then the aqueous solution is transferred into a 15 mL Teflon-lined autoclave and is heated to 150 oC for 8 hours. Finally, the BixSiOy and g-C3N4 are mixed in different ratio in a autoclave and is heated to 150oC for 4 hours. The products are characterized by XRD, SEM-EDS, FE-TEM, HR-XPS, PL, DR-UV, BET, FT-IR, and EPR. inorder to discuss the photocatalytic efficiency of bismuth silicate and bismuth silicate composite g-C3N4. Photocatalytic efficiency of the catalyst is use of photocatalytic degrading of organic pollutants - crystal violet (CV) by measuring crystal violet (CV) concentration.

摘要 I
英文摘要 II
第一章 序論 1
1.1 研究動機 1
1.2 研究目的 4
第二章 文獻回顧 5
2.1染料與染整廢水之特性分類與危害 5
2.1.1染料 5
2.1.2染料的特性與分類 5
2.1.3三苯甲烷類染料.......................................................................7
2.1.4染整廢水之特性與危害...........................................................8
2.2染料廢水處理技術 8
2.2.1 高級氧化程序 9
2.2.2光化學催化氧化法 9
2.3矽酸鉍.............................................................................................10
2.4石墨化氮化碳(g-C3N4) ..................................................................10
第三章 實驗材料與方法 ........................................................................12
3.1實驗流程.........................................................................................12
3.2實驗步驟.........................................................................................13
3.2.1矽酸鉍之製備...........................................................................13
3.2.2石墨化氮化碳(g-C3N4)之製備.................................................13
3.2.3矽酸鉍複合石墨化氮化碳之製備...........................................14
3.3實驗材料與設備.............................................................................14
3.3.1實驗合成材料...........................................................................14
3.3.2染料...........................................................................................15
3.3.3活性物種試劑...........................................................................15
3.4照光程序.........................................................................................16
3.5儀器與分析方法.............................................................................17
3.5.1儀器分析...................................................................................17
3.5.2儀器規格..................................................................................17

第四章 結果與討論 ................................................................................19
4.1 BixSiOy之材料特性分析...............................................................19
4.1.1改變BixSiOy 之合成溫度.......................................................20
4.1.1.1 X射線繞射分析儀........................................................20
4.1.1.2場發式掃描電子顯微鏡/ X光能量分散光譜儀(FE-SEM-EDS)................................................................................22
4.1.1.3場發式穿透電子顯微鏡/X光能量分散光譜儀(FE-TEM-EDS)................................................................................24
4.1.1.4紫外光可見光漫反射光譜儀(UV-visible DRS)..............30
4.1.1.5傅立葉紅外線轉換光譜儀(FT-IR)......................................33
4.1.1.6比表面積測定儀(BET)....................................................35
4.1.1.7 X射線光電子能譜儀(XPS).............................................38
4.1.2改變BixSiOy 之pH值.............................................................42
4.1.2.1 X射線繞射分析儀........................................................42
4.1.2.2場發式掃描電子顯微鏡/ X光能量分散光譜儀(FE-SEM-EDS)................................................................................45
4.1.2.3紫外光可見光漫反射光譜儀(UV-visible DRS).............47
4.1.2.4傅立葉紅外線轉換光譜儀(FT-IR)..................................50
4.1.3改變BixSiOy 鉍和矽之莫耳比...............................................52
4.1.3.1 X射線繞射分析儀........................................................52
4.1.3.2場發式掃描電子顯微鏡/ X光能量分散光譜儀(FE-SEM-EDS)................................................................................57
4.1.3.3紫外光可見光漫反射光譜儀(UV-visible DRS)..............66
4.2 BixSiOy之光催化降解分析...........................................................73
4.2.1 Bi2SiO5晶型矽酸鉍各反應條件下之降解速率....................73
4.2.2 Bi4Si3O12晶型矽酸鉍各反應條件下之降解速率 80
4.2.3 Bi12SiO20晶型矽酸鉍各反應條件下之降解速率 81
4.2.4比較Bi2SiO5、Bi4Si3O12、Bi12SiO20三種晶型矽酸鉍降解速率 85
4.3矽酸鉍複合石墨化氮化碳(Bi2SiO5/g-C3N4) 87
4.3.1 Bi2SiO5/g-C3N4之光催化降解及材料特性分析 87
4.3.1.1 X射線繞射分析儀 87
4.3.1.2場發式掃描電子顯微鏡/ X光能量分散光譜儀(FE-SEM-EDS) 89 4.3.1.3各重量百分比之Bi2SiO5/g-C3N4複合光觸媒降解速率 93
4.3.1.4場發式穿透電子顯微鏡/X光能量分散光譜儀 97
4.3.1.5紫外光可見光漫反射光譜儀 - 10wt.%Bi2SiO5/g-C3N4、Bi2SiO5、g-C3N4特性比較 98
4.3.1.6比表面積測定儀- 10wt.%Bi2SiO5/g-C3N4、Bi2SiO5、g-C3N4特性比較..........................................................................................100
4.3.1.7 X射線光電子能譜儀(XPS)..................................................102
4.3.1.8電子順磁共振圖譜(EPR)-Bi2SiO5/g-C3N4複合光觸媒之自由基檢測..............................................................................................107
4.3.1.9 Bi2SiO5/g-C3N4複合光觸媒活性物種確認..........................108
4.3.1.10光激發螢光光譜(PL)-Bi2SiO5/g-C3N4複合光觸媒之電子-電洞對重組確認..................................................................................111
4.3.1.11紫外光光電子能譜儀(UPS)................................................112
4.3.2觸媒回收之光催化降解活性變化.........................................115
4.3.3 Bi2SiO5/g-C3N4光催化反應機制示意圖...............................116
第五章 結論與建議................................................................................117
5.1 結論.............................................................................................117
5.2 未來方向與建議.........................................................................118
參考文獻..................................................................................................119
表目錄
表 4.1.1改變反應溫度樣品之能帶間隙值 32
表 4.1.2 150℃、200℃、250℃之樣品比表面積、平均孔洞體積及平均孔洞直徑 37
表 4.1.3改變pH值樣品之能帶間隙值 49表 4.1.4矽酸鉍XRD總表 55
表 4.1.5晶相整理表 56
表 4.1.6不同鉍矽莫耳比之矽酸鉍能帶間隙總表(單位eV) 72
表 4.2.1反應速率常數和R2值總表 84
表 4.2.2三晶型矽酸鉍最佳條件反應速率常數和R2值表 86
表 4.3.1反應速率常數和R2值總表 95
表 4.3.2反應速率常數和R2值總表 97
表 4.3.3 Bi2SiO5、g-C3N4、10wt.%Bi2SiO5/g-C3N4樣品之比表面積、平均孔洞體積及平均孔洞直徑..................................................................................102
圖目錄
圖 2.1三苯甲烷母體結構 7
圖 2.2以三聚氰胺合成g-C3N4之過程 11
圖 3.1照光設備 16
圖 4.1.1 BixSiOy在鉍矽比1:1、pH值13時，改變溫度之XRD圖 21
圖 4.1.2左圖為放大10000倍150℃下之Bi12SiO20形貌，右圖為EDS數據 22
圖 4.1.3左圖為放大10000倍200℃下之Bi4Si3O12形貌，右圖為EDS數據 23
圖 4.1.4左圖為放大10000倍250℃下之Bi2SiO5形貌，右圖為EDS數據 23
圖 4.1.5 Bi12SiO20 (加熱150℃、pH值=13、鉍矽比=1:1) 之TEM (a)明場影像圖, (b) SAED擇區電子繞射圖, (c) HR-TEM晶格圖, (d)EDS圖 25圖 4.1.6 Bi4Si3O12 (加熱200℃、pH值=13、鉍矽比=1:1) 之TEM (a)明場影像圖, (b) SAED擇區電子繞射圖, (c) HR-TEM晶格圖, (d)EDS圖 27圖 4.1.7 Bi2SiO5 (加熱250℃、pH值=13、鉍矽比=1:1) 之TEM (a)明場影像圖, (b) SAED擇區電子繞射圖, (c) HR-TEM晶格圖, (d)EDS圖 29圖 4.1.8上圖為改變反應溫度(pH值=13、鉍矽比=1:1)之各晶相矽酸鉍DRS圖譜，下圖為各矽酸鉍樣品之外觀顏色 31圖 4.1.9由公式αhν=A(hν-E)n/2算出之能帶間隙值 32圖 4.1.10改變反應溫度(pH值=13、鉍矽比=1:1)之各晶相矽酸鉍FT-IR圖譜。吸收峰430cm-1為官能基Bi-O 、570cm-1為官能基(SiO4) 4- 、860cm-1為官能基Si-O-Si 、950cm-1 為官能基SiO2、1030cm-1為官能基Si-O、1390cm-1為官能基CO32- 、1635cm-1為分子水molecular water 、3300cm-1為官能基OH- 34圖 4.1.11a 150℃下樣品之等溫氮氣吸脫附圖及孔徑分佈圖 36圖 4.1.11b 200℃下樣品之等溫氮氣吸脫附圖及孔徑分佈圖 36圖 4.1.11c 250℃下樣品之等溫氮氣吸脫附圖及孔徑分佈圖 37圖 4.1.12(a) 150℃(Bi12SiO20) 、200℃(Bi4Si3O12)、250℃(Bi2SiO5 )三種矽酸鉍之XPS全譜圖 39圖 4.1.12(b) 150℃(Bi12SiO20) 、200℃(Bi4Si3O12)、250℃(Bi2SiO5 )三種矽酸鉍之C1s圖 39圖 4.1.12(c) 150℃(Bi12SiO20) 、200℃(Bi4Si3O12)、250℃(Bi2SiO5 )三種矽酸鉍之Bi 4f圖 40
圖 4.1.12(d) 150℃(Bi12SiO20) 、200℃(Bi4Si3O12)、250℃(Bi2SiO5 )三種矽酸鉍之Si 2p圖 40
圖 4.1.12(e) 150℃(Bi12SiO20) 、200℃(Bi4Si3O12)、250℃(Bi2SiO5 )三種矽酸鉍之O1s圖 41圖 4.1.13(a) pH1、pH4、pH7、pH10及pH13之矽酸鉍XRD圖譜(鉍矽比固定1:1，反應溫度固定150℃) 42圖 4.1.13(b) pH1、pH4、pH7、pH10及pH13之矽酸鉍XRD圖譜(鉍矽比固定1:1，反應溫度固定200℃) 43圖 4.1.13(c) pH1、pH4、pH7、pH10及pH13之矽酸鉍XRD圖譜(鉍矽比固定1:1，反應溫度固定250℃) 44圖 4.1.14(a) pH1樣品-Bi6O6(OH)3(NO3)3之SEM圖 46圖 4.1.14(b) pH4樣品-Bi6O6(OH)3(NO3)3之SEM圖 46圖 4.1.15(a) 改變pH 值(溫度固定150℃、鉍矽比=1:1)之各樣品DRS圖譜 48圖 4.1.15(b) 各pH值樣品之外觀顏色 48圖 4.1.15(c) 各pH值之樣品能帶間隙圖譜 49圖 4.1.16各樣品改變pH值(鉍矽比=1:1)之FT-IR圖譜。吸收峰430cm-1為官能基Bi-O 、570cm-1為官能基(SiO4) 4- 、860cm-1為官能基Si-O-Si 、950cm-1 為官能基SiO2、1030cm-1為官能基Si-O、1390cm-1為官能基CO32- 、1450cm-1為官能基O-N-O2-、2360cm-1為官能基CO2 51圖 4.1.17(a) 反應溫度固定150℃，pH值固定pH13，鉍和矽之莫耳比依序為1:1、1:2、1:3、2:1、2:3、3:1、3:2之各晶相矽酸鉍XRD圖譜。 53圖 4.1.17(b) 反應溫度固定200℃，pH值固定pH13，鉍和矽之莫耳比依序為1:1、1:2、1:3、2:1、2:3、3:1、3:2之各晶相矽酸鉍XRD圖譜。 54圖 4.1.17(c) 反應溫度固定250℃，pH值固定pH13，鉍和矽之莫耳比依序為1:1、1:2、1:3、2:1、2:3、3:1、3:2之各晶相矽酸鉍XRD圖譜。 54圖 4.1.18(a) 150℃、pH13、鉍矽莫耳比=1:1，放大10000倍Bi12SiO20之SEM圖及EDS 57圖 4.1.18(b) 150℃、pH13、鉍矽莫耳比=1:2，放大10000倍Bi12SiO20之SEM圖及EDS 57圖 4.1.18(c) 150℃、pH13、鉍矽莫耳比=1:3，放大10000倍Bi2SiO5之SEM圖及EDS 58圖 4.1.18(d) 150℃、pH13、鉍矽莫耳比=2:1，放大10000倍Bi2SiO5之SEM圖及EDS 58圖 4.1.18(e) 150℃、pH13、鉍矽莫耳比=2:3，放大10000倍Bi2SiO5之SEM圖及EDS 58圖 4.1.18(f) 150℃、pH13、鉍矽莫耳比=3:1，放大10000倍Bi12SiO20之SEM圖及EDS 59圖 4.1.18(g) 150℃、pH13、鉍矽莫耳比=3:2，放大10000倍Bi12SiO20之SEM圖及EDS 59圖 4.1.19(a) 200℃、pH13、鉍矽莫耳比=1:1，放大10000倍Bi4Si3O12之SEM圖及EDS 60圖 4.1.19(b) 200℃、pH13、鉍矽莫耳比=1:2，放大50000倍Bi4Si3O12之SEM圖及EDS 60圖 4.1.19(c) 200℃、pH13、鉍矽莫耳比=1:3，放大50000倍Bi4Si3O12之SEM圖及EDS 60圖 4.1.19(d) 200℃、pH13、鉍矽莫耳比=2:1，放大50000倍Bi2SiO5之SEM圖及EDS 61圖 4.1.19(e) 200℃、pH13、鉍矽莫耳比=2:3，放大50000倍Bi2SiO5之SEM圖及EDS 61圖 4.1.19(f) 200℃、pH13、鉍矽莫耳比=3:1，放大50000倍Bi2SiO5之SEM圖及EDS 61圖 4.1.19(g) 200℃、pH13、鉍矽莫耳比=3:2，放大50000倍Bi2SiO5之SEM圖及EDS 62圖 4.1.20(a) 250℃、pH13、鉍矽莫耳比=1:1，放大10000倍Bi2SiO5之SEM圖及EDS 63圖 4.1.20(b) 250℃、pH13、鉍矽莫耳比=1:2，放大10000倍Bi2SiO5之SEM圖及EDS 63圖 4.1.20(c) 250℃、pH13、鉍矽莫耳比=1:3，放大10000倍Bi2SiO5之SEM圖及EDS 63圖 4.1.20(d) 250℃、pH13、鉍矽莫耳比=2:1，放大10000倍Bi2SiO5之SEM圖及EDS 64圖 4.1.20(e) 250℃、pH13、鉍矽莫耳比=2:3，放大10000倍Bi2SiO5之SEM圖及EDS 64圖 4.1.20(f) 250℃、pH13、鉍矽莫耳比=3:1，放大10000倍Bi2SiO5之SEM圖及EDS 64圖 4.1.20(g) 250℃、pH13、鉍矽莫耳比=3:2，放大10000倍Bi2SiO5之SEM圖及EDS 65圖 4.1.21(a) 改變鉍矽莫耳比(pH值固定13、溫度固定150℃)各樣品DRS圖 67圖 4.1.21(b) 150℃各莫耳比樣品之外觀顏色 67圖 4.1.21(c) 150℃各莫耳比樣品之能帶間隙圖譜 68圖 4.1.22(a) 改變鉍矽莫耳比(pH值固定13、溫度固定200℃)各樣品DRS圖 69圖 4.1.22(b) 200℃各莫耳比樣品之外觀顏色 69圖 4.1.22(c) 200℃各莫耳比樣品之能帶間隙圖譜 70圖 4.1.23(a) 改變鉍矽莫耳比(pH值固定13、溫度固定250℃)各樣品DRS圖 71圖 4.1.23(b) 250℃各莫耳比樣品之外觀顏色 71圖 4.1.23(c) 250℃各莫耳比樣品之能帶間隙圖譜 72圖 4.2.1(a) 150℃Bi2SiO5晶型矽酸鉍照射可見光降解結晶紫染料水溶液(crystal violet dye)之光催化速率 74圖 4.2.1(b) 150℃Bi2SiO5晶型矽酸鉍降解結晶紫染料水溶液之反應速率常數和R2值 75圖 4.2.1(c) 200℃Bi2SiO5晶型矽酸鉍照射可見光降解結晶紫染料水溶液(crystal violet dye)之光催化速率 76圖 4.2.1(d) 200℃Bi2SiO5晶型矽酸鉍降解結晶紫染料水溶液之反應速率常數和R2值 77圖 4.2.1(e) 250℃Bi2SiO5晶型矽酸鉍降解結晶紫染料水溶液之光催化速率 78圖 4.2.1(f) 250℃Bi2SiO5晶型矽酸鉍降解結晶紫染料水溶液之反應速率常數和R2值 79圖 4.2.2(a) Bi4Si3O12晶型矽酸鉍降解結晶紫染料水溶液之光催化速率 80圖 4.2.2(b) Bi4Si3O12晶型矽酸鉍降解結晶紫染料水溶液之反應速率常數和R2值 81圖 4.2.3(a) Bi12SiO20晶型矽酸鉍降解結晶紫染料水溶液之光催化速率 82圖 4.2.3(b) Bi12SiO20晶型矽酸鉍降解結晶紫染料水溶液之反應速率常數和R2值 83圖 4.2.4(a) Bi2SiO5、Bi4Si3O12、Bi12SiO20三種晶型矽酸鉍降解結晶紫染料水溶液之光催化速率 85圖 4.2.4(b) Bi2SiO5、Bi4Si3O12、Bi12SiO20三種晶型矽酸鉍降解結晶紫染料水溶液之反應速率常數和R2值 86
圖 4.3.1不同重量百分比Bi2SiO5/g-C3N4之圖譜 88
圖 4.3.2(a) 單純Bi2SiO5 (鉍:矽=2:1，pH=13，合成溫度=150oC) 樣品形貌及EDS 90圖 4.3.2(b) 單純g-C3N4樣品形貌及EDS 90圖 4.3.2(c) 1wt.% Bi2SiO5/g-C3N4樣品形貌及EDS 90圖 4.3.2(d) 5wt.% Bi2SiO5/g-C3N4樣品形貌及EDS 91圖 4.3.2(e) 7wt.% Bi2SiO5/g-C3N4樣品形貌及EDS 91圖 4.3.2(f) 10wt.% Bi2SiO5/g-C3N4樣品形貌及EDS 91圖 4.3.2(g) 20wt.% Bi2SiO5/g-C3N4樣品形貌及EDS 92圖 4.3.2(h) 50wt.% Bi2SiO5/g-C3N4樣品形貌及EDS 92圖 4.3.3(a) 各重量百分比之Bi2SiO5/g-C3N4複合光觸媒照射可見光降解結晶紫染料水溶液之光催化速率圖 94圖 4.3.3(b) 各重量百分比之Bi2SiO5/g-C3N4複合光觸媒照射可見光降解結晶紫染料水溶液之反應速率常數和R2值 94圖 4.3.4(a) 10wt.%Bi2SiO5/g-C3N4、Bi2SiO5、g-C3N4光催化實驗數據比較圖 96圖 4.3.4(b) 10wt.%Bi2SiO5/g-C3N4、Bi2SiO5、g-C3N4之反應速率常數和R2 96圖 4.3.5 10wt.%Bi2SiO5/g-C3N4樣品之TEM影像 98圖 4.3.6(a) 10wt.%Bi2SiO5/g-C3N4、Bi2SiO5、g-C3N4之DRS比較圖 99圖 4.3.6(b) 各樣品之外觀顏色 99圖 4.3.6(c) 各樣品之能帶間隙圖譜............................................................100圖 4.3.7(a) Bi2SiO5 (b) g-C3N4 (c) 10wt.%Bi2SiO5/g-C3N4之等溫氮氣吸脫附圖及孔徑分佈圖..........................................................................................101圖 4.3.8(a) g-C3N4、Bi2SiO5和Bi2SiO5/g-C3N4樣品的XPS全譜圖.............104
圖 4.3.8(b) C 1s高解析光譜圖......................................................................104
圖 4.3.8(c) N 1s高解析光譜圖..............................................................105
圖 4.3.8(d) O 1s高解析光譜圖..............................................................105
圖 4.3.8(e) Bi4f高解析光譜圖...............................................................106
圖 4.3.8(f) Si2p高解析光譜圖...............................................................106
圖 4.3.9(a) DMPO․OH EPR圖譜.......................................................107
圖 4.3.9(b) DMPO․O2- EPR圖譜........................................................108
圖 4.3.10(a)添加不同的自由基移除劑之降解結晶紫染料水溶液速率..............................................................................................................109 圖 4.3.10(b) 添加不同自由基移除劑之降解結晶紫染料水溶液速率圓柱圖..........................................................................................................110
圖 4.3.11 Bi2SiO5、g-C3N4、Bi2SiO5/g-C3N4之PL光譜圖......................112
圖 4.3.12(a) g-C3N4的UPS圖................................................................113
圖 4.3.12(b) Bi2SiO5的UPS圖.................................................................114
圖 4.3.13 10wt%Bi2SiO5/g-C3N4複合光觸媒回收之光催化降解效率圖..............................................................................................................115
圖 4.3.14 Bi2SiO5/g-C3N4光催化反應機制示意圖............................116

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