臺灣博碩士論文加值系統

本研究製備氧化石墨烯與兩種不同特性半導體複合材料，並研究其光催化活性。首先，自製氧化石墨烯，再於固定溫度下以水熱反應合成一系列氧化石墨烯/硫化鋅(G-ZnS_x)、氧化石墨烯/氧化亞銅(G-Cu2O_y)複合材料，分析前驅物種類與濃度、水熱反應時間等製程參數對光觸媒特性與光活性之影響，以亞甲基藍水溶液光催化脫色及二氧化碳光催化還原反應評估光觸媒材料之光活性。
研究結果顯示，以水熱法製備出之氧化石墨烯/硫化鋅複合材料皆具有閃鋅礦(sphalerite)晶型；透過Scherrer’s formula計算出硫化鋅粒徑大小約為15 ~ 25 nm，與TEM影像觀察之結果一致；由SEM影像及TGA結果可發現，隨著硫化鋅前驅物濃度的提升，氧化石墨烯上覆蓋之硫化鋅量隨之增加。XPS圖譜則發現，氧化石墨烯/硫化鋅複合材料除了ZnS之主要成分，亦含有少量ZnO及S8。由UV-VIS圖譜之能隙估算結果發現，氧化石墨烯的存在將使氧化石墨烯/硫化鋅複合材料發生紅位移之現象。螢光光譜結果證實，添加氧化石墨烯能有效地抑制電子電洞對再結合速率，將有助於光電子轉移至反應物，進而提升氧化石墨烯/硫化鋅複合材料的光催化效率。藉由自由基捕捉實驗可發現隨著硫化鋅含量增加，氫氧自由基產生量亦提升。另一方面以氧化亞銅直接與氧化石墨烯進行水熱程序所得之G-Cu2O-y，在自由基捕捉實驗則是顯示含水熱時間6小時所得之G-Cu2O-0.05可最快速的產生最大量氫氧自由基；G-Cu2O-y系列觸媒隨著水熱時間與氧化亞銅添加量增加，氧化石墨烯表面銅的價數會由一價轉為二價，顯示銅的價態與含量將影響光催化活性。
以波長為254 nm的UV燈為光源，進行亞甲基藍水溶液的光催化脫色反應，實驗結果顯示添加氧化石墨烯可有效提升脫色效率。二氧化碳光催化還原反應結果顯示，一系列G-ZnS_x觸媒在水氣存在下，可將二氧化碳轉化為甲醇、甲醛、一氧化碳及微量的氫氣與甲烷。G-ZnS_0.05觸媒顯現最高之光催化活性，產物中以甲醛的產量最高；相同金屬比例下，G-ZnS-x對二氧化碳的還原效率優於G-Cu2O-y。

摘要 i
Abstract iii
致謝 v
目錄 vii
圖目錄 xi
表目錄 xviii
第一章 緒論 1
1-1 前言 1
1-2 研究動機與目的 3
第二章 文獻回顧 5
2-1 光觸媒簡介 5
2-2 光觸媒反應機制 8
2-3 二氧化碳之減量與反應 13
2-3-1 二氧化碳簡介 13
2-3-2 二氧化碳處理方式 15
2-3-3 光催化還原二氧化碳之文獻回顧 19
2-4 硫化鋅光觸媒 25
2-4-1 硫化鋅之結構與性質 25
2-4-2 硫化鋅之製備方法 27
2-4-3 硫化鋅之光催化活性 29
2-5 氧化亞銅光觸媒 38
2-5-1 氧化亞銅之結構與性質 38
2-5-2 氧化亞銅之製備方法 39
2-5-3 氧化亞銅之光催化活性 40
2-6 石墨烯簡介 45
2-6-1 石墨烯之特性 45
2-6-2 石墨烯之製備與合成方法 46
2-6-3 化學脫層法製備氧化石墨烯 47
2-7 石墨烯複合材料 50
第三章 實驗方法 61
3-1 藥品與儀器設備 61
3-1-1 實驗藥品 61
3-1-2 儀器型號與規格 63
3-2 實驗步驟 66
3-2-1 氧化石墨烯之製備 66
3-2-2 氧化石墨烯/硫化鋅複合材料之製備 67
3-2-3 氧化石墨烯/氧化亞銅複合材料之製備 67
3-2-4 樣品代號說明 68
3-3 觸媒特性分析原理與方法 70
3-3-1 高解析X光繞射儀(XRD) 70
3-3-2 X光光電子能譜 (XPS) 72
3-3-3 場發射掃描式電子顯微鏡(SEM) 74
3-3-4 場發射穿透式電子顯微鏡(TEM) 76
3-3-5 能量散射光譜儀(EDS) 77
3-3-6 紫外光-可見光光譜儀(UV-VIS) 78
3-3-7 螢光光譜儀(Fluorescence) 81
3-3-8 電子順磁共振儀(EPR) 83
3-3-9 氣相層析儀(GC) 86
3-4 光催化活性檢測 90
3-4-1 亞甲基藍(Methylene Blue)之光催化脫色 90
3-4-2 二氧化碳之光催化還原 95
4-1 觸媒之特性分析 98
4-1-1 XRD圖譜分析 98
4-1-2 TEM影像分析 106
4-1-3 SEM影像分析 116
4-1-4 XPS圖譜分析 120
4-1-5 UV-VIS吸收光譜分析 122
4-1-6 螢光光譜分析 131
4-1-7 EPR分析 133
4-2 觸媒之光催化活性檢測 139
4-2-1 亞甲基藍(Methylene Blue)之光催化脫色反應 139
4-2-2 二氧化碳之光催化還原反應 144
第五章 結論 152
參考文獻 154
附錄 168

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