臺灣博碩士論文加值系統

鑭系元素擁有空的電子軌域使之對近紅外光譜具有吸收能力，因此添加鑭系元素對半導體光觸媒利用長波長光譜(λ>600 nm)進行光催化具有良好的效果。本研究先利用熱裂解(thermal decomposition method)製備氧化鉍粉體，並以此氧化鉍粉體進行沉澱法(precipitation)與光化學還原法(photoreduction)披覆不同濃度比例(1 mol%、3 mol%)鐠、釓於氧化鉍粉體表面，隨後進行煆燒使披覆於外層的鐠、釓提高結晶度。利用XRD、FESEM、UV-VIS、PL及利用甲基澄為汙染試劑進行可見光光催化活性檢測(λ>420 nm)，其結果顯示相對於沉澱法披覆不均的形況，光化學還原法披覆氧化鉍可形成核殼結構，且披覆釓、鐠可有效降低電子電洞對再結合率使光催化活性上升，並透過光催化活性得知披覆濃度於1 mol%為最佳條件，濃度過高並無助於複合粉體吸收長波長光譜使光觸媒特性得以提升。此外， 以600°C為煆燒溫度，複合粉體可放出最佳之螢光強度，並且透過晶粒尺寸變化可得知當煆燒溫度上升所披覆鐠、釓將擴散至氧化鉍晶界，抑制其晶粒大小與結晶結構之變化。

Semiconductors can be expected to exhibit excellent photocatalytic effects under light irradiation at a wavelength longer than 600 nm by coating lanthanide. In our study, bismuth oxide particles were first synthesized via thermal decomposition； and subsequently, lanthanides, such as praseodymium (Pr) and gadolinium (Gd), were coated in different concentrations (1 mol% and 3 mol%) onto the surface of the bismuth oxide by precipitation and photochemical reduction methods. Finally, the as-coated powders were calcined at 600°C in air for 1 h to improve the crystallinity of Pr and Gd. The material characteristics were determined by X-ray diffractometry (XRD), scanning electron microscopy (SEM), UV-visible, photoluminescence (PL). And, methylation reagent was used as an representative organic pollutant to evaluate the photocatalytic activity of the composite powders under visible light irradiation (λ>420 nm).The morphology of precipitated coatings was unevenly distributed；Whereas, the morphology of photoreduced coating exhibited a core shell structure. The photocatalytic activity of bismuth oxide powder can be expected to be increased by coating Pr and Gd to enhance the electron-hole pair separation. Highest photocatalytic activity of bismuth oxide was obtained by coating 1.0 mol% lanthanide. Coating higher concentration of lanthanides, however, was not useful for the powders to absorb light in the long-wavelength region to improve the photocatalytic activity. In addition strongest fluorescence emission intensity was obtained by calcining the powder at 600°C. By observing the microstructural change, diffusion of the coated Pr and Gd in grain boundary of bismuth oxide influenced the grain size and crystal structure when the calcination temperature was elevated.

中文摘要 I
ABSTRACT II
目錄 II
圖目錄 VIII
表目錄 XIII
第一章、 前言 1
第二章、 文獻回顧 2
2.1光觸媒 2
2.1.1光觸媒的介紹與原理 2
2.1.2光觸媒的光催化特性 3
2.1.3半導體光觸媒材料及改質方法 5
2.1.4光觸媒受光催化效能 9
2.1.5國內研究光觸媒之現況 12
2.2氧化鉍 14
2.2.1氧化鉍結構與特性 14
2.2.2氧化鉍的製備 17
2.3上轉換 22
2.3.1上轉換(upconversion)機制 22
2.3.2鑭系 27
2.3.3 TiO2利用鑭系元素之改質 28
2.3.4 Bi2O3利用鑭系元素之改質 33
第三章、 實驗步驟 35
3.1實驗目的與做法 35
3.2光觸媒粉體製備 36
3.2.1熱裂解法製備氧化鉍粉體 36
3.2.2沉澱法披覆鑭系結構 38
3.2.3光化學還原法披覆鑭系結構 41
3.3觸媒材料之特性分析 43
3.3.1熱重分析 43
3.3.2 X光繞射分析 43
3.3.3冷場發射掃描式電子顯微鏡表面形態分析 45
3.3.4穿透式電子顯微鏡粉體結構分析 45
3.3.5可見光-紫外光譜分析儀 45
3.3.6高解析比表面積分析儀 46
3.3.7螢光光譜分析儀 47
3.4光催化降解檢測 48
第四章、 結果與討論 49
4.1熱裂解熱處理前粉體之特性分析 49
4.1.1 TGA熱重分析 49
4.1.2 X光繞射分析 50
4.1.3 FESEM 表面結構分析 51
4.2熱裂解法複合粉體之特性分析 52
4.2.1 X光繞射分析 52
4.2.1.1沉澱法披覆 53
4.2.1.2光化學還原法披覆 57
4.2.3 FESEM表面結構分析 60
4.2.3.1沉澱法披覆 61
4.2.3.2光化學還原法披覆 64
4.2.4 HRTEM粉體顯微結構分析 68
4.2.4.1沉澱法披覆 68
4.2.4.2光化學還原法披覆 69
4.2.5 UV-Visible光學特性分析 71
4.2.5.1沉澱法披覆 72
4.2.5.2光化學還原法披覆 74
4.2.6 BET分析 76
4.2.6.1沉澱法披覆 76
4.2.6.2光化學還原法披覆 77
4.2.7螢光光譜分析 78
4.2.7.1沉澱法披覆 79
4.2.7.2光化學還原法披覆 81
4.3光催化活性分析 83
4.4綜合比較 85
4.4.1 晶粒大小對光催化活性之影響 85
4.4.2 比表面積對光催化活性之影響 86
4.4.3 螢光放光強度對光催化活性之影響 87
4.4.4溫度對Bi2O3複合粉體之影響 88
4.4.4.1 X光繞射分析 88
4.4.4.2 螢光光譜分析 90
4.4.4.3 光催化分析 91
4.5 上轉換檢測 92
第五章、 結論 93
第六章、 未來方向 94
參考文獻 95

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