- 學位論文
孔洞性金屬有機凝膠及金屬有機骨架之合成與鑑定研究
Synthesis and characterizations of porous metal-organic gels and metal organic frameworks
摘要
摘要 本論文主要是以金屬離子Cr3+分別與配位基(ligand) 4,4'-聯苯基二甲酸 (4,4'-biphenyldicarboxylic acid, H2BPDC)、2,6-萘二甲酸(2,6-naphthalenedicarboxylic acid, H2NDC)和溶劑N,N-二甲基甲醯胺(N,N-dimethylformamide, DMF) 水熱反應，合成出2種金屬有機凝膠(metal–organic gels, MOGs) CrMOG1 及CrMOG2，並以4種不同方式進行MOGs活化，1.使用乙醇（ETOH）置換DMF 後，以超臨界CO2置換ETOH，2. ETOH置換DMF 後烘乾，3.以DMF清洗去除多餘的金屬及配位基，再加熱移除DMF，4.以超臨界CO2移除DMF，最後再將產物烘乾。 另以Ga3+與H2BPDC水熱反應，合成出與文獻DUT-5具有相似結構之金屬有機骨架(metal organic framework, MOF)孔洞材料[Ga (OH)(BPDC)]，經過DMF溶劑置換後，以烘乾方式進行活化。 經由上述各種活化方式去除孔洞內溶劑後，由測定其N2氣體吸附性（BET）判斷孔洞特性，結果發現MOGs具有不規則孔洞，MOF為具有規則排列之孔洞；在結構鑑定上，以粉末X-ray繞射分析儀(PXRD)來鑑定；利用熱重分析測定樣品熱重損失，SEM觀察材料外觀形狀與尺寸等，來探討化合物特性。
並列摘要
Abstract The purpose of this thesis is mainly on the hydrothermal reaction of the metal ion, Cr3+,with the ligands, 4,4'-biphenyldi-carboxylic acid(H2BPDC) , 2,6-naphthalenedicarboxylicacid(H2NDC), and solvent N,N-dimethyl -formamide (DMF) respectively. Two metal-organic gels (MOGs), CrMOG1 and CrMOG2, were synthesized and activated in four different methods: 1. After ethanol （ETOH）replaces DMF, use supercritical CO2 to replace ETOH. 2. use ETOH to replace DMF, then dries it. 3. use DMF to wash out the excess metals and ligands, and then remove DMF by heating them. 4. remove DMF with supercritical CO2 and then dry them. Besides, porous materials of the metal organic framework (MOF), structurally similar to DUT-5 [Ga(OH)(BPDC)]in some references, can be synthesized from the hydrothermal reaction of Ga3+and H2BPDC. Drying after the replacement with DMF can activate the porous materials. After removing the solvents inside the pores by the above-mentioned activation methods, the physical results show that pores of the MOGs are arranged irregularly and the MOF are arranged regularly by means of the measurement of the properties of the gas adsorption (BET) of N2. Otherwise, three methods are brought to study the characteristics of the compounds: Powder X-ray diffraction spectrometry (PXRD) is for the structure determination; thermal gravimetric analyzer (TGA) is for the weight loss; and SEM is for the observation of the shapes and sizes of the materials.