本研究製備氧化鐵/石墨相氮化碳光觸媒，應用於有機染料在可見光下的降解。採用單一前驅物尿素的熱裂解合成原型石墨相氮化碳，並透過添加不同比例的甲酸銨、丙二醯胺或草酸與尿素搭配，合成一系列改性的石墨相氮化碳，再利用水熱法將石墨相氮化碳與氧化鐵結合，形成氧化鐵/石墨相氮化碳複合物。研究中使用電子顯微鏡觀察光觸媒的形貌與微結構，X光繞射儀鑑定其晶體結構，紫外光可見光光譜儀測量其光學性質。染料羅丹明B光催化降解的實驗結果顯示，相較於原型石墨相氮化碳，改性的石墨相氮化碳有較好的光催化活性，其中又以丙二醯胺改性的石墨相氮化碳表現最為優異；將此改性的石墨相氮化碳與氧化鐵結合，可進一步增強其光催化活性，在可見光下照射30分鐘，染料降解率達91%，而且此複合光觸媒也具有良好的穩定性與可重複使用性。

This study details the preparation of iron oxide/graphitic carbon nitride (Fe2O3/g-CN) composites for the photocatalytic degradation of organic dye under visible light. The original g-CN was synthesized by the pyrolysis of a single precursor, urea. A series of modified g-CN photocatalysts were also prepared by using double precursors. The three precursor compounds chosen to pair with urea were ammonium formate, malonamide, and oxalic acid. Subsequently, the best performing modified g-CN was combined with iron oxide through a hydrothermal process to form iron oxide/g-CN composites. The morphology and microstructure of the as-prepared photocatalysts were studied by scanning and transmission electron microscopy. Their crystal structures and optical properties were investigated by X-ray diffraction analysis and ultraviolet-visible spectrometry, respectively. Based on the experimental results from the photocatalytic degradation of rhodamine B (RhB), the modified g-CN catalysts perform better than the original one. Among the modified g-CN, those modified with malonamide exhibited the highest photocatalytic activity. Further enhancement in photocatalytic activity can be achieved when the malonamide-modified g-CN is combined with iron oxide to form heterojunctions. The resulting Fe2O3/g-CN composite shows excellent photocatalytic activity, degrading 91% of RhB in 30 min under visible white light. In addition, the composite photocatalyst also has good stability and reusability.

摘 要 i
ABSTRACT ii
誌 謝 iv
目 錄 v
圖目錄 viii
表目錄 x
第一章 緒論 1
1.1 前言 1
1.2 研究動機與目的 2
第二章 研究背景與文獻回顧 3
2.1 光觸媒起源與發展 3
2.2 光觸媒原理 5
2.3 石墨相氮化碳材料結構與特性 8
2.4 石墨相氮化碳製備方法 9
2.4.1 固相反應法(Solid Phase Reaction) 9
2.4.2 溶劑熱法(Solvothermal) 10
2.4.3 電化學沉積法(Electrodeposition) 10
2.4.4 熱聚合法(Thermal Polymerization) 10
2.5 石墨相氮化碳的改性 11
2.5.1 形貌調控 11
2.5.2 元素摻雜 12
2.5.3 表面修飾 12
2.5.4 半導體異質結 13
2.6 氧化鐵結構與特性 14
2.7 氧化鐵製備方法 16
2.7.1 水解法(Hydrolysis) 16
2.7.2 水熱法(Hydrothermal) 16
2.7.3 溶膠-凝膠法(Sol-Gel Method) 17
2.7.4 噴霧熱分解法(Spray Pyrolysis) 18
2.7.5 沉澱法(Precipitation) 18
2.7.6 微乳液法(Microemulsion) 19
2.8 染料簡介 19
2.8.1 染料結構之組成 19
2.8.2 染料的危害 20
2.8.3 羅丹明B (Rhodamine B，Rh B)的結構與特性 23
2.9 影響光催化的因素 25
第三章 材料與實驗方法 28
3.1 實驗藥品 28
3.2 實驗儀器 29
3.3 儀器分析原理 30
3.3.1 掃描式電子顯微鏡 (Scanning electron microscope, SEM) 30
3.3.2 穿透式電子顯微鏡 (Transmission electron microscope, TEM) 31
3.3.3 X光繞射分析儀 (X-ray diffraction, XRD) 32
3.3.4 螢光光譜儀 (Photoluminescence Spectroscopy，PL) 33
3.3.5 紫外線/可見光分光光譜儀 (UV–vis spectroscopy，UV-Vis) 34
3.4 實驗方法 35
3.4.1 實驗架構 35
3.4.2 石墨相氮化碳之製備 36
3.4.3 改性之石墨相氮化碳之製備 37
3.4.4 樹葉狀氧化鐵之製備 38
3.4.5 氧化鐵/石墨相氮化碳複合材料之合成 39
3.4.6 光催化降解染料實驗 40
3.4.7 重複使用性實驗 41
3.4.8 自由基捕捉實驗 42
第四章 結果與討論 43
4.1 石墨相氮化碳之定性分析 43
4.1.1 石墨相氮化碳之形貌 (SEM、TEM) 43
4.1.2 X-射線繞射 (XRD)之分析 48
4.2 光催化染料降解 50
4.2.1 光催化染料降解測試結果 50
4.2.2 紫外光-可見光散射光譜 55
4.2.3 光致發光光譜 (PL) 57
4.2.4 重複使用性測試 59
4.3光催化降解機制 60
4.3.1 自由基捕捉實驗 60
4.3.2 光催化染料降解機制圖 61
第五章 結論 62
參考文獻 63

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