以拉曼光譜研究金屬有機骨架碳化反應之活化能

本研究主要為使用拉曼光譜技術，探討金屬有機骨架碳化過程之反應速率。金屬有機骨架選擇了相同中心金屬系列的MIL-100(Al)、MIL-53(Al)、MIL-69(Al)、DUT-4(Al) 和CYCU-4(Al)。這些金屬有機骨架分子結構不同。MIL-100為籠狀孔洞結構，其他金屬有機骨架為菱形孔洞結構。孔洞與比表面積大小不同。配位基種類也不同。碳化金屬有機骨架使用拉曼量測D band與G band強度，我們利用D band對G band面積比值對處理金屬有機骨架碳化時間之趨勢，求得一級反應速率，再利用反應速率對處理碳化溫度之變化以Arrhenius equation計算得反應之活化能。在金屬有機骨架碳化後，我們發現有針狀晶體生成物。我們施以HF酸洗後，這些針狀晶體會被去除，加上能量色散型X射線光譜儀鑑定，因此我們斷定針狀晶體屬於金屬氧化物及其他殘餘的無機化合物。利用場發射掃描式電子顯微鏡及X-光粉末繞射儀探討新的針狀晶體化合物，我們確認了以上之結論。有關碳化金屬有機骨架在拉曼光譜、活化能、場發射掃描式電子顯微鏡、X-光粉末繞射儀的實驗數據結果之關聯性，我們將會有詳細的討論。

關鍵字

金屬有機骨架,碳化,活化能,拉曼

並列摘要

This study explored the reaction rates of the carbonization process of metal-organic frameworks using Raman spectroscopy. The metal-organic frameworks of MIL-100(Al), MIL-53(Al), MIL-69(Al), DUT-4(Al), and CYCU-4(Al) of the same metal center series were selected. These metal-organic frameworks have different molecular structures. MIL-100 is of cage-like porous structure, while other metal-organic frameworks are of diamond-shaped porous structure. The pore and specific surface areas, as well as the ligand types, are different. Raman spectroscopy was used to measure the intensity of D and G bands of the carbonized metal-organic frameworks. The area ratio of the D band to the G band versus the carbonization time trend of processing metal-organic frameworks was used to obtain the first order reaction rate. The changes of the reaction rate versus the carbonization processing temperature were used to obtain the activation energy of the reaction by Arrhenius equation. The needle-shaped crystal products were found after the carbonization of the metal-organic frameworks. The needle-shaped crystals were removed after the HF treatment. EDS identification was also conducted. The results showed that needle-shaped crystals belong to metal oxide and other residual inorganic compounds. The finding confirmed that FESEM and Powder X-ray Diffraction could be used to explore the new needle-shaped crystal compounds. The correlation of the data of the Raman spectrum, activation energy, FESEM, and Powder X-ray Diffraction experiments of the carbonized metal-organic frameworks were discussed in detail.

並列關鍵字

metal–organic frameworks,carbonization,Raman,activation energy

參考文獻

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以拉曼光譜研究金屬有機骨架碳化反應之活化能

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