小角度與廣角 X-ray 散射分析金屬有機框架材料之孔洞結構

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林韋承(Wei-cheng Lin) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

小角度與廣角 X-ray 散射分析金屬有機框架材料之孔洞結構
(Pore Structures of Metal-Organic Frameworks by Small-Angle and Wide-Angle X-ray Scattering)

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摘要(中)

在本研究當中，利用小角度與廣角散射技術來分析不同合成路徑的Cu-BTC金屬有機框架材料 (HKUST-1) 中不同尺度的孔洞結構。我們的目標是建立一套快速且低成本的方法，有效的量測出孔洞材料的比表面積，並進一步了解當水氣自HKUST-1孔洞中移除後的結構演變。主要的分析樣品為編號M700及Nano-sized，兩種樣品皆由工研院合作同仁合成提供，並利用已量產的商業化樣品 (編號C300) 作為比較的對象。動態 (in-situ) 的小角度與廣角散射量測資訊顯示出HKUST-1隨著溫度上升，水氣自材料孔洞中移除對其結構與晶相有著明顯的改變，藉由Beaucage模型擬合小角度散射曲線可將孔洞尺寸分佈以及比表面積做完整的定量分析，擬合結果指出不同層級的孔洞結構與比表面積有著一定程度的相依性，此分析技術可以使得我們了解在HKUST-1結構中何種尺度的孔洞是造成二氧化碳吸脫附循環性質好壞的關鍵。另外一方面，在廣角散射圖譜中有局部性的訊號增強，結合小角度散射的分析資訊綜合可知訊號增強是來自於除去HKUST-1孔洞中水氣以及晶粒成長的影響。廣角散射曲線利用GSAS套裝軟體進行結構重組，更可定量的顯現出當除去HKUST-1孔洞中水氣後會使晶格常數以及銅離子之間的間距縮短。

摘要(英)

In this investigation, small-angle and wide-angle X-ray scattering (SAXS & WAXS) measurements were utilized to analyze porous structures at different scales for Cu-BTC metal-organic frameworks (HKUST-1) of varied size populations prepared by different synthesis routes. Our objective is to establish a fast and low-cost method for effectively measuring specific surface area of pores, and to understand the change of HKUST-1’s structure after dehydration. Two kinds of HKUST-1, M700 and Nano-size, were provided by ITRI. An in-situ SAXS/WAXS experiment demonstrates the effect of temperature on the concurrent evolutions of pore structure and crystal phase during the removal of water upon heating. The results were also compared to the commercial sample (C300). By simulation modeling of SAXS profiles, the pore size distribution and specific surface area could be quantitatively determined. Quantitative curve analysis of SAXS indicates that the hierarchical pore structures of MOFs have the size-dependent specific surface areas. This gives us more insights in understanding which scale of pore size within MOFs is dominant for controlling the ability of CO2 adsorption. On the other hand, HKUST-1 shows special peak intensity enhancement in WAXS result. Dehydration and grain growth are the two main reasons. GSAS refinement also reveals that the lattice constants and the Cu-Cu distance decreased after dehydration.

關鍵字(中)

★ 小角度
★ 金屬有機框架材料
★ 孔洞
★ 比表面積

關鍵字(英)

★ Small-Angle X-ray Scattering (SAXS)
★ Wide-Angle X-ray Scattering (WAXS)
★ Metal-organic framework (MOF)
★ HKUST-1
★ Pore Structure

論文目次

摘要 .................................................. i
Abstract.............................................. ii
致謝 ................................................ iii目錄 ................................................. iv
圖目錄 .............................................. vii
表目錄 ............................................... xi
第一章緒論 ........................................... 1
1.1 孔洞材料簡介 ...................................... 1
1.2 金屬有機框架材料之開發與應用 ........................ 3
1.3 結構解析之重要性 ................................... 6
1.4 MOFs 材料穩定性 ................................... 8
1.5 實驗動機 ......................................... 10
第二章實驗方法 ...................................... 11
2.1 實驗藥品 ......................................... 11
2.2 樣品製備 ......................................... 13
2.2.1 二氧化碳吸脫附循環 .............................. 13
2.2.2 熱處理 ........................................ 14
2.3 使用儀器.......................................... 14
2.3.1 小角度 X 光散射 (SAXS) ......................... 15
2.3.2 比表面計算 ..................................... 19
2.3.3 Rietveld 結構精算法 ............................ 20
2.3.4 場發射掃描式電子顯微鏡 (FE-SEM) ................. 22
2.3.5 熱分析 (TGA & DSC) ............................ 24
2.3.6 傅立葉轉換紅外線光譜儀 (FT-IR) .................. 25
第三章結果與討論 ..................................... 26
3.1 HKUST-1 基本性質 ................................. 26
3.1.1 比表面積量測資訊 ................................ 26
3.1.2 二氧化碳吸脫附循環量測資訊 ....................... 26
3.2 SAXS 變溫臨場量測 - 中孔洞結構解析與比表面積計算 .... 27
3.2.1 HKUST-1 中孔洞結構解析技術建立 .................. 27
3.2.2 SAXS 臨場觀察中孔洞結構變化 ..................... 29
3.2.3 比表面積理論計算及分佈之探討 ..................... 32
3.3 WAXS 變溫臨場量測 - 溫度對 HKUST-1 結構之影響及GSAS 結構精算分析 .............................................. 34
3.3.1 CO 2 吸脫附循環及溫度對 HKUST-1 繞射訊號之影響 ... 34
3.3.2 GSAS 結構精算分析 .............................. 40
第四章結論 .......................................... 43
Future Work .......................................... 45
參考資料 .............................................. 46
附錄 ................................................. 53
附錄 1 – SAXS 圖譜 1D 擬合結果 (Beaucage model) ........ 53
附錄 2 – SAXS 理論計算比表面積分析之斜率擬合結果 ......... 55
附錄 3 – 口試投影片 ................................... 57

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指導教授

孫亞賢(Ya-sen Sun)

審核日期

2015-7-29

推文