鋯金屬有機骨架無序到結晶化的快速轉換

Abstract

本論文研究鋯金屬有機骨架 (Metal-Organic Framework, MOF) 從無序化到有序化快速轉換的過程，主要討論UiO-66、UiO-66-NH2和MOF-808這三個MOF。第一部分研究發現，鋯金屬MOF合成後的產物在尚未純化以及活化前，在溶劑中為非結晶態。通過雙溶劑置換（TOSE）和真空下加熱（HEVA）進行MOF合成的後處理，在PXRD圖可以看到晶相訊號的確有從弱到強的現象，也就是MOF從非晶相轉為晶相，且當反應時間縮短時，雙溶劑置換和真空下加熱的後處理方式也使MOF具有一定的結晶性。第二部分針對加熱反應方式進行探討，將烘箱改爲加熱攪拌，證明了這種一般的加熱反應方式相對烘箱加熱，可以更縮短反應時間時、容易量產化，也可使MOF具有好的結晶性，且比表面積與文獻資料沒有明顯差異。第三部分，文獻中雙溶劑置換的方式有簡單滴管清洗、室溫攪拌、加熱攪拌等，此處進一步討論了不同雙溶劑置換方式對MOF的影響，結果顯示室溫攪拌清洗的方式不利於缺陷的修復甚至破壞MOF的結晶性。

This research investigates the rapid transition process of zirconium-based Metal-Organic Frameworks (MOFs) from disorder to order. The main focus of the study is on three MOFs: UiO-66, UiO-66-NH2, and MOF-808.Firstly, it was found that the synthesized products of metal-based MOFs were amorphous in the solvent before purification and activation. Through the study found that by using the two solvent exchange (TOSE) and heat under vacuum (HEVA), MOFs can be observed a phenomenon of crystal phase signals increasing from weak to strong by PXRD, indicating that MOFs have transformed from the amorphous phase to the crystalline phase. Moreover, when the reaction time is shortened, the post-treatment methods of dual-solvent exchange and vacuum heating also contribute to the crystallinity of MOFs.Secondly, the heating reaction method is investigated by replacing the oven synthesis with heating and stirring synthesis. This approach demonstrates that this method compared to oven heating, allows for shorter reaction times, facilitates mass production, and results in MOFs with good crystallinity. Additionally, there are the same with specific surface area compared to the data reported in the literature.Thirdly, various purification methods for two solvent exchange, such as simple pipet washed, room-temperature washed, and heated stirring, are discussed in the study. We examine the impact of different purification methods on MOFs. The results show that the results show that room temperature stirring for two solvent exchange is unlikely to the repair the defects of the MOF.