以鋁、銦為中心金屬之孔洞材料合成與性質研究

Syntheses and Properties of Aluminum- and Indium-Based Porous Material

李元瀚(Yuan-Han LI)

指導教授 ： 王素蘭

國立清華大學/理學院/化學系所/博士(2018年)

摘要

本論文包含6個化合物的合成、結構與性質研究，其中4個為以In原子為中心金屬的二維MOFs孔洞材料，2個為以Al原子為中心金屬的MOFs孔洞材料。所有化合物的晶體結構皆以單晶X光繞射儀收集數據後進行結構解析，以粉末X光繞射圖譜比對理論圖譜確定樣品純度後，再進行氣體吸附與光學性質的測量。依照不同的金屬中心、結構相關性可分為A、B兩個系統討論：
系統A中，有別於MOFs中常以三維的孔洞材料進行氣體吸附或選擇性的研究，本論文合成出4個二維的MOFs結構(A1-A4)，其中A1與A2具有氣體選擇性，這是在過文獻中以In原子為中心金屬的MOFs未曾見到的結果，為第一個具有氣體選擇性的二維MOFs孔洞材料。而化合物A4也具有良好的二氧化碳固定化的效果，其轉化率可達到98%。
系統B改以Al3+為中心金屬，分別合成出具有不同維度的MOFs材料，及結構鑑定利用粉墨X光繞射做結構解析。其中CAU8-ODB為一個三維的孔洞材料，由CAU8-ODB進行高壓CO2 與CH4的吸附實驗顯示出CAU8-ODB具有非常好的高壓CH4的特性，有別於文獻必需設計特殊官能基才能具有良好的吸附性質，CAU8-ODB僅以市售可得的有機官能基便可具有良好的吸附性，是文獻中少見的。

關鍵字

金屬有機骨架化合物 ； 氣體吸附 ； 水熱合成

並列摘要

The synthesis, structural characterization, and gas sorption and catalytic properties of six novel compounds are included in this thesis. Among them, four are Indium metal-organic frameworks, two are Aluminum metal-organic frameworks. The crystal structures and chemical formulas for all compounds were determined primarily by single-crystal and powder X-ray diffraction analysis. Based on correlations between synthesis and structure, these ten compounds are grouped into A and B systems for discussion.
System A consists of four compounds: (Me2NH2)[In(SBA)2] (1) ,(Me2NH2)[In(SBA)(BDC)] (2), (Me2NH2)[In(SBA)(BDC- NH2)] (3), and (NH4)3[In3Cl2(BPDC)5] (4), (H2SBA = 4,4'-sulfonyldibenzoic acid; H2BDC= 1,4-benzenedicarboxylic acid; H2BDC-NH2 =2-amino-1,4-benzenedicarboxylic acid;H2BPDC = 4,4'-biphenyldicarboxylic acid) have been synthesized under solvothermal reaction conditions for compound 1 to 3 and DES (deep eutectic solvent) reaction for compound 4. The structure of these MOFs has been determined by usingsingle crystal X-ray diffraction study and theses four 2D monolayer framework withporous properties.The N2 gas sorption measurements indicated that Brunauer–Emmer–Teller(BET) and Langmuir surface areas of compound 1 are 207 and 301 m2 g-1respectively which is probably the first one having substantial gas uptake properties in the entire 2D In-MOFs family to date. Furthermore, these new indium MOFs on the addition of n-Bu4NBr were active for the cycloaddition of CO2 and propylene oxide, generating propylene carbonates in high conversions under mild conditions. Particularly, the most active MOF 4 was found to efficiently couple CO2 with a series of terminal epoxides to give the corresponding cyclic organic carbonates with high selectivities.
System B presents two are Aluminum metal-organic frameworks. [Al(HODB)(OH)] and [Al(ODB)(OH)]. Both of the [Al(HODB)(OH)] structure and [Al(ODB)(OH)] was refined from powder X-ray diffraction data, A thorough characterization shows that the [Al(ODB)(OH)] is stable up to 350 °C in air, almost independent of the linker molecules incorporated. The former MOFs are porous toward N2 and CO2. The compound [Al(ODB)(OH)] not only has the selectivity for CO2/N2 but also have the high pressure CO2 and CH4 adsorption properties.

並列關鍵字

Metal organic framework ； Gas adsorption ； Hydrothermal Synthesis

參考文獻

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