溶劑脫附誘導鋁金屬有機骨架之快速結晶合成研究

Abstract

在金屬有機骨架(Metal-Organic Frameworks, MOF) 材料的結構前瞻晶體工程研究開發中，第四代MOF的非序化以及缺陷結構特徵，大幅提升MOF建構骨架的自由度。本研究以加熱抽真空的溶劑脫附方式，快速驅動MOF從無序化結晶成有序孔洞結構，並且聚焦於鋁MOF孔洞材料在溶劑脫附誘導快速結晶化的優化反應參數研究。 研究分成三個部分，在第一部分中，探討三種不同有機配位基，在加熱反應後經由雙溶劑置換下，透過加熱抽真空的溶劑快速脫附方法，可誘導鋁MOF之快速結晶化，同時大幅縮短反應時間至三十分鐘來合成MIL-68等結構MOF，並且觀察到晶格非序化(Amorphous)結構因溶劑脫附誘發快速結晶(Crystalline)的過程。 第二及第三部分中，研究反應參數優化得到Al-SDC-68及Al-DMDA-68兩個MOF的最佳條件，在Al-SDC-68系統中之MOF B10具有最高BET比表面積2585 m2/g，孔徑分布為15.2及27.2 Å；在Al-DMDA-68系統中之MOF C12具最高BET比表面積2505 m2/g，孔徑分布18.6及31.7Å。 本論文精細研究，釐清了過去不曾討論過的反應細節，確認結合「溶劑置換」和「加熱抽真空」的關鍵方法，才能夠實現奈米晶種快速聚集且結晶化。未來研究展望，將可開發應用在MOF工業化製備、奈米複合材料與製備MOF薄膜等不同領域。In the structural prospective crystal engineering research and development of Metal-Organic Frameworks (MOF) materials, the disordered and defect structure characteristics of the fourth-generation MOF greatly increase the degree of freedom of MOF construction. In this study, the solvent desorption method by heating under vacuuming quickly drives the MOF from disordered amorphous to crystalline structure, and focuses on the optimization of reaction parameters of porous aluminum MOF in the solvent desorption-induced rapid crystallization.The research is divided into three parts. In the first part, three different organic ligands are discussed. After the heating reaction, the rapid solvent desorption method of heating under vacuum through the double solvent washing can induce the rapid crystallization of aluminum MOF and greatly shorten the reaction time to 30 minutes to synthesize MIL-68 MOF analogues, and it was observed that the amorphous structure induced rapid crystallization due to solvent desorption. In the second and third parts, the optimal conditions for the two MOFs of Al-SDC-68 and Al-DMDA-68 were obtained by studying the optimization of reaction parameters. The MOF B10 in the Al-SDC-68 system has the highest BET specific surface area of 2585 m2/g, the pore size distribution is 15.2 and 27.2 Å; the MOF C12 in the Al-DMDA-68 system has the highest BET specific surface area of 2505 m2/g, and the pore size distribution is 18.6 and 31.7 Å. The detailed research of this thesis has clarified the key of the reaction that have not been discussed in the past, and confirmed that the combination of the methods of"solvent replacement" and "heating and vacuuming" can achieve rapid aggregation and crystallization of nano nucleation. Future research prospects can be developed and applied in different fields such as the industrial preparation of MOF, nanocomposites and the preparation of MOF films.