臺灣博碩士論文加值系統

本研究以高壓水熱法(hydrothermal methods)合成矽酸鉍〈Bi12SiO20〉及複合Bi12SiO20/GO(氧化石墨烯)及Bi12SiO20/g-C3N4(石墨化氮化碳)，並探討其光催化降解之成效。矽酸鉍是以硝酸鉍及矽酸鈉當起始物，並加入3M NaOH調整pH值至13.3，然後將該水溶液轉移到15毫升高壓釜中，加熱至100℃4小時。矽酸鉍複合氧化石墨烯是將Bi12SiO20和GO依不同重量百分比，混合在高壓釜中加熱至100℃4小時。矽酸鉍複合石墨化氮化碳是將不同重量百分比的Bi12SiO20和石墨化氮化碳( g-C3N4)，混合在高壓釜中加熱至100℃4小時。合成觸媒樣品以高解析X光繞射儀(HR-XRD)、場發式掃描電子顯微鏡附能量分散光譜儀(FE-SEM-EDS)、場發式穿透電子顯微鏡附能量分散光譜儀(FE-TEM-EDS)、高解析度X光光電子能譜儀(HR-XPS)、紫外光-可見光擴散反射光譜儀(UV-vis DRS)、比表面積分析儀(BET)、螢光光譜儀(PL)、電子順磁共振光譜儀(EPR)等儀器分析產物的組成。
本研究使用結晶紫(CV)染料與2-羥基苯甲酸(2-hydroxybenzoic acid))作為標的汙染技術物。合成的Bi12SiO20觸媒降解結晶紫(CV)染料的速率k值原本只有0.005 h-1 ，但複合Bi12SiO20/20wt%-GO樣品與5wt%-Bi12SiO20/g-C3N4最高降解速率k值分別為0.050 h-1與0.078 h-1 ，且樣品經複合後對於降解速率都有著正向的效果。最佳觸媒樣品對於無色染料2-羥基苯甲酸(2-hydroxybenzoic acid)染料，也同樣具有光催化效果，以此推測觸媒樣品光催化與光敏化的反應機制，最後透過活性物種測試，以作為光觸媒降解結晶染料之研究基礎。

In this study, bismuth silicate and bismuth silicate composite graphene oxide (GO) and composite graphitic carbon nitride (g-C3N4) are prepared using autoclave hydrothermal methods. The novel heterojunctions of Bi12SiO20/GO and Bi12SiO20/g-C3N4 are fabricated by the hydrothermal method for the first time. Bismuth silicate is prepared by Bi(NO3)3 and Na2SiO3, dissolved in an 3M NaOH aqueous solution and adjusted the pH value . The aqueous solution is then transferred into a 15 mL Teflon-lined autoclave and heated to 100oC for 4 hours. Bi12SiO20/GO or Bi12SiO20/g-C3N4 is mixed in different weight ratio independently in a autoclave and heated to 100 oC for 4hours. The products are characterized by XRD, SEM-EDS, FE-TEM, HR-XPS, PL, DR-UV, BET, FT-IR, and EPR. To discuss bismuth silicate and bismuth silicate composite with graphene oxide and graphitic carbon nitride for photocatalytic efficiency, photocatalytic efficiency of the catalyst is used for the photocatalytic degradation of organic pollutants - crystal violet (CV) and 2-hydroxybenzoic acid . The measurement of crystal violet (CV) concentration, that the reaction rate constant k of Bi12SiO20 / 20wt%-GO and 5wt%-Bi12SiO20/g-C3N4 is 0.050h-1 and 0.078 h-1, respectively. This study shows that the ratio of Bi12SiO20：GO and Bi12SiO20： g-C3N4 strongly affect composite morphology, light response and photocatalytic activity.

目錄
第一章 緒論 1
1.1 研究動機 1
1.2 研究目的 2
第二章 文獻回顧 3
2.1 染料 3
2.2光催化反應與高級氧化程序 5
2.3矽酸鉍 6
2.4氧化石墨烯 7
2.5石墨化氮化碳〈g-C3N4〉 8
第三章 實驗材料與方法 9
3.1實驗研究流程 9
3.2 觸媒合成方法 10
3.2.1矽酸鉍之製備〈Bi12SiO20〉 10
3.2.2氧化石墨稀之製備 11
3.2.3矽酸鉍複合氧化石墨稀之製備 12
3.2.4石墨化氮化碳(g-C3N4)之製備 13
3.2.5矽酸鉍複合石墨化氮化碳之製備 14
3.3 實驗材料與設備 15
3.3.1 實驗合成材料 15
3.3.2 活性物種試劑 15
3.3.3 有機汙染物 16
3.4 照光程序 17
3.5 儀器與分析方法 18
3.5.1儀器分析: 18
3.5.2儀器規格: 18
3.6活性物種測定實驗 20
第四章 結果與討論 21
4.1 合成Bi12SiO20光觸媒 21
4.1.1高解析X射線繞射分析儀 (HD-XRD) 21
4.1.2場發式掃描電子顯微鏡/ X光能量分散光譜儀(FE-SEM-EDS) 26
4.1.3傅立葉紅外線轉換光譜儀(FT-IR) 28
4.1.4高解析度X光光電子能譜儀(HR-XPS) 29
4.1.5 比表面積分析(BET) 32
4.2 合成Bi12SiO20/GO光觸媒降解結晶紫染料 34
4.2.1 高解析X射線繞射分析儀 (HD-XRD) 34
4.2.2場發式掃描電子顯微鏡/ X光能量分散光譜儀(FE-SEM-EDS) 36
4.2.3 場發式穿透電子顯微鏡附能量分散光譜儀(FE-TEM-EDS) 40
4.2.4 傅立葉紅外線轉換光譜儀(FT-IR) 42
4.2.5紫外光-可見光擴散反射光譜儀(UV-vis DRS) 45
4.2.6高解析度X光光電子能譜儀(HR-XPS) 47
4.2.6螢光光譜儀 (PL) 52
4.2.7比表面積分析(BET) 53
4.2.8光二極體陣列式紫外光-可見光光譜儀(UV-vis PDA) 55
4.2.9 Bi12SiO20/20wt%-GO光觸媒之回收率與穩定性 61
4.2.10 Bi12SiO20/20wt%-GO光觸媒之活性物種確認 63
4.2.11 電子順磁共振光譜儀(EPR) 65
4.2.12 Bi12SiO20/20wt%-GO光觸媒之電子電洞轉移機制圖 68
4.3 合成Bi12SiO20/g-C3N4光觸媒降解結晶紫染料 70
4.3.1 高解析X射線繞射分析儀 (HD-XRD) 70
4.3.2場發式掃描電子顯微鏡/ X光能量分散光譜儀(FE-SEM-EDS) 72
4.3.3 場發式穿透電子顯微鏡附能量分散光譜儀(FE-TEM-EDS) 76
4.3.4 傅立葉紅外線轉換光譜儀(FT-IR) 78
4.3.5紫外光-可見光擴散反射光譜儀(UV-vis DRS) 81
4.3.6高解析度X光光電子能譜儀(HR-XPS) 83
4.3.6螢光光譜儀 (PL) 88
4.3.7比表面積分析(BET) 89
4.3.8光二極體陣列式紫外光-可見光光譜儀(UV-vis PDA) 91
4.3.9 5wt％-Bi12SiO20/ g-C3N4光觸媒之回收率與穩定性 96
4.3.10 5wt％-Bi12SiO20/ g-C3N4光觸媒之活性物種確認 98
4.3.11 電子順磁共振光譜儀(EPR) 100
4.3.12 5wt％-Bi12SiO20/g-C3N4光觸媒之電子電洞轉移機制圖 102
第五章：結論 104
參考文獻 106

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