臺灣博碩士論文加值系統

在本實驗中，藉由甘胺酸燃燒法(Glycine Nitrate Process，GNP)的方式，以不同甘胺酸對硝酸根的比例(G/N)，製備了具有尖晶石(Spinel)結構的ZnFe2O4和ZnO-ZnFe2O4粉末催化劑，¬利用於甲醇水蒸氣重組(SRM)。透過SEM、TEM可知，以GNP合成之ZnFe2O4和ZnO-ZnFe2O4粉末催化劑具有多孔結構且藉由SAED進行晶體鑑定。另外，從BET比表面積吸脫附分析發現，在G/N 1.5時，比表面積依序為5.66 m2/g (ZnFe2O4)、8.20 m2/g (ZnO-ZnFe2O4)；G/N 1.7時，依序為6.03 m2/g (ZnFe2O4)、11.67 m2/g (ZnO-ZnFe2O4)，可得Spinel結構受到G/N的影響並不大，並屬於Type IV 型中的H3型遲滯迴線等溫線。此外，SRM實驗中，發現ZnFe2O4在450°C以及ZnO-ZnFe2O4在500°C下，有最佳的催化效果；尤其，500°C下的ZnO-ZnFe2O4最高H2生成速率為6663 ml STP min-1 g-cat-1。並透過H2-TPR分析其在不同溫度範圍的氫氣還原情況。另一方面，ZnO-ZnFe2O4 (GN=1.7)有良好的H2選擇性和穩定性。因此，希望藉由研究ZnFe2O4(純相Spinel)和ZnO-ZnFe2O4(複合粉末)，來了解Spinel的高催化活性及ZnO良好的分散性以利提高催化劑的比表面積，對於未來蒸汽重組運用在民生工業上有更進一步的發展。

In this experiment, ZnFe2O4 (spinel structure) was prepared by the glycine nitrate method (GNP) with different glycine to nitrate ratios (G/N). And ZnO-ZnFe2O4 powder catalyst for steam reforming methanol (SRM). It could be seen by SEM and TEM that the GNP-synthesized ZnFe2O4 and ZnO-ZnFe2O4 powder catalysts had a porous structure, and the crystals were identified by SAED. In addition, from the adsorption and desorption analysis of BET specific surface area, it was found that when G/N was 1.5, the specific surface area was 5.66 m2/g (ZnFe2O4) and 8.20 m2/g (ZnO-ZnFe2O4) in sequence. When G/N was 1.7, in sequence are 6.03 m2/g (ZnFe2O4) and 11.67 m2/g (ZnO-ZnFe2O4), the Spinel structure was not greatly affected by G/N, and belonged to the H3-type hysteresis loop isotherm in Type IV. On the other hand, it was found that ZnFe2O4 had the best catalytic effect at 450°C and ZnO-ZnFe2O4 at 500°C in the SRM experiment. Especially, the highest H2 generation rate of ZnO-ZnFe2O4 at 500°C was about 6600 ml STP min-1 g-cat-1. Then, the hydrogen reduction in different temperature ranges was analyzed by H2-TPR. On the other hand, ZnO-ZnFe2O4 had good H2 selectivity and stability. Therefore, it was hoped that studying ZnFe2O4 (pure phase) and ZnO-ZnFe2O4 (composite powder). We could understand the high catalytic activity of Spinel and the good dispersibility of ZnO to improve the specific surface area of the catalyst. It had been further development in the human livelihood industry.

摘 要 i
ABSTRACT ii
致 謝 iv
圖目錄 viii
表目錄 xi
Chapter 1 前言 1
Chapter 2 文獻回顧 3
2.1 尖晶石結構 Spinel structure 3
2.2 氧化鋅 Zinc oxide 5
2.3 甘胺酸燃燒製備氧化物方法Glycine-Nitrate Process 6
2.4 甲醇水蒸氣重建 Methanol steam reforming 8
Chapter 3 實驗部分 10
3.1 實驗藥品及其來源 10
3.2 實驗氣體及其來源 11
3.3 ZnFe2O4和ZnO-ZnFe2O4複合催化劑的製備 12
3.4 甲醇水蒸氣重組系統 15
3.4.1 ZnFe2O4和ZnO-ZnFe2O4粉末在N2氣氛中的熱處理 15
3.4.2 甲醇水蒸氣重建產氫反應模式 17
3.5 性質分析 18
3.5.1 X射線繞射分析儀 18
3.5.2 掃描式電子顯微鏡 20
3.5.3 穿透式電子顯微鏡 22
3.5.4 比表面積測定 24
3.5.5 程序升溫還原 27
3.5.6 氣相層析儀 28
Chapter 4 結果與討論 31
4.1 ZnFe2O4和ZnO-ZnFe2O4粉末之XRD分析 31
4.2 ZnFe2O4和ZnO-ZnFe2O4粉末之SEM分析 33
4.3 ZnFe2O4和ZnO-ZnFe2O4粉末之TEM分析 35
4.4 ZnFe2O4和ZnO-ZnFe2O4粉末之STEM/EDS分析 37
4.5 ZnFe2O4和ZnO-ZnFe2O4粉末之BET分析 41
4.6 H2-TPR分析 44
4.7 ZnFe2O4和ZnO-ZnFe2O4粉末在催化還原(SRM)後性質分析 46
4.7.1 ZnFe2O4和ZnO-ZnFe2O4粉末在SRM後XRD分析 46
4.7.2 ZnFe2O4和ZnO-ZnFe2O4粉末在SRM後SEM分析 48
4.7.3 ZnFe2O4和ZnO-ZnFe2O4粉末之氣相層析分析 50
4.8 結論 56
Chapter 5 製備多孔性結構CuGd2O4粉末應用在紫外光光降解RhB 57
5.1 前言 57
5.2 實驗部分 59
5.2.1 實驗藥品來源 59
5.2.2 實驗光來源 59
5.2.3 前驅物製備及實驗流程 60
5.2.4 CuGd2O4光催化劑紫外光降解羅丹明B 62
5.2.5 特徵分析 63
5.2.5.1 傅立葉轉換紅外光譜儀 (FT-IR) 63
5.2.5.2 紫外-可見分子吸收光譜 66
5.3 結果與討論 69
5.3.1 CuGd2O4粉末之XRD分析 69
5.3.2 CuGd2O4粉末之FT-IR分析 71
5.3.3 CuGd2O4粉末之SEM分析 73
5.3.4 CuGd2O4粉末之TEM分析 75
5.3.5 CuGd2O4粉末之STEM-EDX分析 77
5.3.6 以燃燒法製備之粉末與其在氮氣環境退火後之BET分析 79
5.3.7 以燃燒法製備之粉末與其在氮氣環境退火後光學特性分析 錯誤! 尚未定義書籤。
5.3.8 CuGd2O4催化劑光降解RhB之特性分析 83
5.4 結論 88
總結 89
Reference 90
Paper Publication and Conference Presentations 100

 
圖目錄
圖 2.1 尖晶石晶體結構: Fm m對稱性空間群 4
圖 2.2 氧化鋅之六方晶和立方晶之晶體結構 5
圖 2.3 甘胺酸之化學結構圖 6
圖 3.1 透過甘胺酸燃燒法製備前驅液粉末及分析模式示意圖 13
圖 3.2 甘胺酸燃燒法的反應流程 14
圖 3.3 管狀爐中催化劑放置示意圖 16
圖 3.4 甲醇水蒸氣重建反應裝置示意圖 17
圖 3.5 Bruker D2 Phaser X-ray diffraction meter 19
圖 3.6 SEM Hitachi Regulus 8100 20
圖 3.7 鍍金機 21
圖 3.8 穿透式電子顯微鏡Field emission transmission electron microscope, JEOL JEM-2100F (FE-TEM) 23
圖 3.9 Brunauer-Emmett-Teller analyzer 26
圖 3.10 The Schematic of temperature programmed reduction (TPR) 27
圖 3.11 GC 1000 氣相層析儀 29
圖 3.12 GC分析後的峰值 29
圖 3.13 檢量線曲線 30
圖 4.1 (a) ZnO-ZnFe2O4 G/N 1.5, (b) ZnO-ZnFe2O4 G/N 1.7, (c) ZnFe2O4 G/N 1.5, (d) ZnFe2O4 G/N 1.7 粉末的XRD圖譜。 32
圖 4.2 (a), (b) ZnFe2O4 (G/N 1.5) (c), (d) ZnFe2O4 (G/N 1.7) (e), (f) ZnO-ZnFe2O4 (G/N 1.5) (g), (h) ZnO-ZnFe2O4 (G/N 1.7) 為SEM分析圖。 34
圖 4.3 ZnFe2O4粉末之(a)TEM圖及(b) HRTEM圖 36
圖 4.4 ZnFe2O4粉末之(a)選區繞射圖和(b)模擬繞射圖 36
圖 4.5 透過GNP法製備的ZnFe2O4粉末的STEM-EDS圖像和元素分布圖 (a) STEM 圖像 (b) Zn (c) Fe (d) O (e) Zn、Fe和O重疊的元素分布圖。 38
圖 4.6 GNP法製備ZnO-ZnFe2O4粉末的STEM-EDS圖像和元素分佈圖 (a) STEM 圖像 (b) Zn (c) O (d) Fe (e) Zn、Fe和O重疊的元素分佈圖。 39
圖 4.7 在500°C下還原處理後ZnO-ZnFe2O4的STEM元素分布圖像 (a) STEM圖像 (b) Zn (c) Fe (d) O (e) Zn、Fe和O的元素分布圖。 40
圖 4.8 (a)-(d) N2吸附/脫附曲線和 (e) GNP製備的ZnFe2O4和ZnO-ZnFe2O4粉末的孔徑分佈。 43
圖 4.9 H2-TPR分析圖 (a) ZnFe2O4 GN=1.5, (b) ZnFe2O4 GN=1.7, (c) ZnO- ZnFe2O4 GN=1.5, (d) ZnO- ZnFe2O4 GN=1.7。 45
圖 4.10 蒸汽重建後GNP法製備ZnFe2O4和ZnO-ZnFe2O4粉末的XRD圖譜。 47
圖 4.11 在SRM反應後 (a), (b) ZnFe2O4 (G/N 1.5) (c), (d) ZnFe2O4 (G/N 1.7) (e), (f) ZnO-ZnFe2O4 (G/N 1.5) (g), (h) ZnO-ZnFe2O4 (G/N 1.7) 粉末之SEM圖 49
圖 4.12 ZnFe2O4 and ZnO-ZnFe2O4催化劑在350-500°C下之氫氣產量圖。 52
圖 4.13 ZnO-ZnFe2O4 (GN=1.7)催化劑在500℃下時效處理表現。 53
圖 4.13 (a) H2, (b) CH4, (c) CO 和 (d) ZnO-ZnFe2O4 (GN=1.7)催化劑在350-500℃下的CO2選擇性/轉化率 55
圖 5.1 以甘胺酸燃燒合成法製備CuGd2O4粉末實驗流程圖 61
圖 5.2 RhB光降解示意圖。 62
圖 5.3 傅立葉轉換紅外光譜儀(FT-IR)工作原理示意圖。 64
圖 5.4 Bruker OPTIK GmbH Rudolf-Plank-Str.27. 65
圖 5.5 分光光度計簡易工作原理示意圖 67
圖 5.6 UV-Visble spectrometer (Shimadzu UV2600). 68
圖 5.7 利用GNP法製備的CuGd2O4的XRD圖譜。 70
圖 5.8 GNP法製備的CuGd2O4粉末的FTIR分析。 72
圖 5.9 CuGd2O4粉末在不同放大倍率下的SEM圖。 74
圖 5.10 CuGd2O4的(a) TEM、(b) HRTEM圖像、(c) FFT繞射圖(d)模擬繞射圖。 76
圖 5.11 透過GNP法製備的CuGd2O4粉末的STEM-EDS圖像和元素分布 (a) STEM 圖像(b) Cu (c) Gd (d) O (e) Cu、Gd和O的元素分布圖。 78
圖 5.12 (a) N2吸附/脫附曲線和(b)粉末的孔徑分佈。 80
圖 5.13 CuGd2O4粉末之UV-Visible光譜 (內圖為CuGd2O4 為能隙估計值) 82
圖 5.14 RhB光降解機制理示意圖。 85
圖 5.15 （a）無（b）CuGd2O4催化劑對RhB光降解的吸光度。 86
圖 5.16 ln(C/C0)與光降解時間的速率常數圖。 87

 
表目錄
表 4 1 GNP法製備的ZnFe2O4和ZnO-ZnFe2O4粉末的比表面積。 42
表 4 2 ZnFe2O4 and ZnO-ZnFe2O4催化劑在不同溫度下(350-500°C)之氫氣產量表 52
表 5 1 在不同銅基尖晶石結構的比表面積比較[64]，[65]。 79
表 5 2 不同光催化劑的速率常數 (k) 比較。 85

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