臺灣博碩士論文加值系統

本實驗利用水熱法製備硫化銅-氧硫化鋅/石墨氮化碳(g-C3N4)之有機-無機奈米複合異質結構光觸媒，並展現出良好的應光催化產氫效率。透過調整氧硫化鋅製程條件、硝酸銅前驅液濃度及石墨氮化碳添加量，製備一系列光觸媒，並利用FESEM、XRD、FETEM、XPS、DRS、螢光光譜儀、電化學阻抗頻譜及SECM等儀器探討其表面型態、晶型結構、表面化學、光學性質及材料之光電流效應結果。最佳條件ZG25N5之光觸媒在紫外光照射下產氫效率為12200 μmol g－1h－1。硫化銅-氧硫化鋅/石墨氮化碳有良好的光觸媒特性，包含硫化銅的修飾幫助能隙的降低及增強吸光特性，可激發出更多的電子電洞對，再藉由石墨氮化碳導電特性及比表面積的提升，光電子經石墨氮化碳的導引，有效增加電子電洞分離率，進而提升光催化產氫效率。
本實驗第二部分，新穎的光催化產氫研究以氧硫化鋅及氧硫化鋅/石墨烯光觸媒，搭配甘油進行實驗。利用FESEM, XRD, FETEM, XPS, DRS、電化學阻抗頻譜、螢光光譜及SECM等儀器進行材料分析及討論。最佳條件ZG5之光觸媒在40% 甘油水溶液中經紫外光照射下產氫效率為1070 μmol g－1h－1。石墨烯的混摻有助於光電子藉由氧硫化鋅/石墨烯接觸之交界面進行導引，有效增加電子電洞分離率，增強了光催化劑的光催化活性。ZG5光觸媒展現卓越的光觸媒活性，是因為其有效提升比表面積、電子電洞對分離及光吸收強度。

In this study, CuS-ZnS1-xOx/g-C3N4 organic-inorganic heterostructured nanocomposite which was prepared by means of a hydrothermal method, exhibited good activities for photocatalytic hydrogen production. Effects of the ZnS1-xOx process condition, Cu(NO3)2 precursor concentration and g-C3N4 content on the morphology, crystalline properties, optical property, surface chemistry and photocurrent were investigated by using field-emission scanning electron microscope (FESEM), X-ray diffraction (XRD), field-emission transmission electron microscopy (FETEM), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible diffuse reflectance spectra (DRS), Photoluminescence (PL), electrochemistry impedance spectroscopy (EIS), photocurrent response, and hydrogen production tests. The optimized photocatalytic H2 production rates of ZC25N5I photocatalyst under UV light irradiation reach 12200 μmol g-1h-1. CuS-ZnS1-xOx/g-C3N4 photocatalysts have excellent properties, including decreased bandgap and enhanced light absorption due to CuS helping and increased specific surface area and efficient charge separation resulting from incorporation of g-C3N4.
In second part, the photocatalytic reforming of glycerol to hydrogen at room temperature by zincoxysulfide, zincoxysulfide/graphene catalysts was investigated. The photocatalysts were characterized by FESEM, XRD, FETEM, XPS, DRS, EIS, PL, photoelectrochemical test, and photocatalytic H2 production tests. The photocatalytic H2 production rates of ZG5 photocatalyst in 40% glycerol solution under UV light irradiation reach 1070 μmol g-1h-1.Incorporation of graphene helps the separation of photogenerated charge through the zincoxysulfide/graphene interfaces and enhance the photocatalytic activity of the photocatalysts. The ZG5 photocatalysts improved superior activity because of increased specific surface area, efficient charge separation, and enhanced light absorption.

摘要 i
Abstract iii
目錄 iv
圖目錄 vi
表目錄 viii
第一章 緒論 1
1.1 前言 1
1.2 研究動機與目的 2
第二章 基本理論及文獻回顧 4
2.1 光觸媒產氫原理 4
2.1.1 Z-Scheme之分解水產氫方式 5
2.2光觸媒降解原理 7
2.3半導體 8
2.4 光觸媒 14
2.4.1 氧化鋅(ZnO) 14
2.4.2 硫化鋅(ZnS) 17
2.4.3 硫化銅(CuS)基本性質 21
2.5 石墨氮化碳 21
2.6 光觸媒改質 25
第三章 實驗藥品與步驟 27
3-1實驗藥品及配件 27
3-2實驗儀器 28
3-3實驗流程圖 30
3-4實驗步驟 31
3.4.1 氧化鋅光觸媒製備 31
3.4.2硫化銅修飾氧硫化鋅光觸媒製備 31
3.4.3 石墨氮化碳製備 31
3.4.4 硫化銅修飾氧硫化鋅/石墨氮化碳複合觸媒 32
3.4.5 產氫實驗 32
3.5 實驗樣品命名 32
3.6 實驗分析及鑑定 34
3.6.1 冷場發射掃描式電子顯微鏡及輛散佈光譜儀(FESEM) 34
3.6.2 場發射穿透式電子顯微鏡(FETEM) 35
3.6.3 多功能薄膜X 光繞射儀(HRXRD) 37
3.6.4 化學分析電子能譜儀(XPS) 38
3.6.5 反射式紫外光/可見光光譜儀(UV/Vis Spectrometer) 39
第四章 結果與討論 41
4.1硫化銅-氧硫化鋅/石墨氮化碳 41
4.1.1 光觸媒-表面結構、元素及分佈(冷場發射掃描式電子顯微鏡 FESEM、EDX、mapping) 41
4.1.2 X射線繞射光譜 (XRD) 45
4.1.3穿透式電子顯微鏡 (TEM分析) 46
4.1.4 表面化學性質 (化學分析電子能譜儀 XPS分析) 47
4.1.5擴散反射式紫外線-可見光譜 (DRS) 49
4.1.6 光觸媒之產氫效率 50
4.1.7 光電流 (Photocurrent) 55
4.1.8 螢光光譜分析 (PL) 57
4.1.9 電化學阻抗頻譜 (EIS) 58
4.2氧硫化鋅/石墨烯 59
4.2.1 光觸媒-表面結構、元素及分佈(冷場發射掃描式電子顯微鏡 FESEM、EDX、mapping) 59
4.2.2 X射線繞射光譜 (XRD) 61
4.2.3穿透式電子顯微鏡 (TEM分析) 62
4.2.4擴散反射式紫外線-可見光譜 (DRS) 63
4.2.5 光觸媒之產氫效率 64
4.2.6 光電流 (Photocurrent) 69
4.2.7 螢光光譜分析 (PL) 70
4.2.8 電化學阻抗頻譜 (EIS) 71
第五章 結論 73
第六章 參考資料 75

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