混合配位基鋁金屬有機骨架之合成與結構轉換之研究

本研究論文中，使用金屬試劑三氯化鋁(AlCl3)與混合配位基H2DMDA (4,4'-((1E,1'E)-hydrazine-1,2-iylidenebis(methanylylidene)) dibenzoic acid)及H2TzDB (4,4'-(1,2,4,5-tetrazine-3,6-diyl)dibenzoic acid)來合成孔洞性鋁金屬有機骨架化合物(Al-MOFs)。以二甲基甲醯胺(DMF)作為溶劑所合成之MOF具有結構缺陷(Al-MOF-53)，透過低沸點的溶劑丙酮(Acetone)置換乾燥後，可以使結構重新排列形成剛性高孔洞性有機骨架(Al-MOF-68)。為了瞭解合成晶體構造之轉變，使用了粉末X-ray繞射(PXRD)來鑑定化合物結構。使用氮氣吸脫附儀分析MOF孔徑大小與分布。本研究藉由固定金屬試劑與配位基的莫耳數條件下，調控兩種混合配位基H2DMDA及H2TzDB的比例，來合成孔洞性鋁金屬有機骨架化合物。經由最佳合成與活化方式後得到較佳的結構結晶性以及比表面積大小，實驗結果發現H2DMDA(100%)：H2TzDB(0%)之比表面積為2698.0 m2/g、吸附量為950 cm3/g，H2DMDA(75%)：H2TzDB(25%)比表面積為969.46 m2/g、吸附量為380 cm3/g，H2DMDA(50%)：H2TzDB(50%)之比表面積為2507.9 m2/g、吸附量為920 cm3/g，H2DMDA(25%)：H2TzDB(75%)之比表面積為328.4 m2/g、吸附量為900 cm3/g。配位基比例為H2DMDA(100%)：H2TzDB(0%)之比表面積及吸附量都較佳。

關鍵字

混合配位基；金屬有機骨架材料

並列摘要

In this research, the metal reagent aluminum trichloride (AlCl3) and the mixed ligand H2DMDA (4,4'-((1E,1'E)-hydrazine- 1,2-iylidenebis(methanylylidene))dibenzoic acid) and H2TzDB (4,4'-(1,2,4,5-tetrazine-3,6-diyl)dibenzoic acid) are used to synthesize porous aluminum metal organic frameworks(Al-MOFs). The MOFs synthesized with dimethylformamide (DMF) as a solvent has structural defects (Al-MOF-53). After solvent exchange and vacuum drying by the low boiling point solvent, acetone, the MOF structure can be rearranged to form rigid and high porosity new MOF (Al-MOF-68). In order to understand the transformation of synthetic crystal structure, powder X-ray diffraction (PXRD) was used to identify the structure of the compound. The pore size distribution of MOF was analyzed using a nitrogen adsorption and desorption instrument. In this study, a series of porous aluminum metal organic frameworks were synthesized by adjusting the ratio of the two mixed ligands (H2DMDA and H2TzDB)with 100/0(1Y), 75/25(2Y), 50/50(3Y), 25/75(4Y). After the best synthesis and activation conditions, better structure crystallinity and specific surface area were obtained. The experimental results found that the specific surface area of 1Y is 2698.0m2/g and the adsorption capacity is 950cm3/g. 2Y has a specific surface area of 969.46m2/g and an adsorption capacity of 380cm3/g. 3Y has a specific surface area of 2507.9m2/g and an adsorption capacity of 920cm3/g, 4Y has a specific surface area of 328.4m2/g and an adsorption capacity of 900cm3/g. The proportion of ligands by 1Y has better specific surface area and adsorption capacity.