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    Please use this identifier to cite or link to this item: http://ir.lib.ncu.edu.tw/handle/987654321/70325

    Title: 含多吡啶有機配子之多孔性金屬有機配位聚合物自組裝合成、結構鑑定與氣體吸附性質研究;Self-Assembly, Structures, Gas Adsorption and Applications of Porous Metal–Organic Frameworks Constructed from Multi-pyridyl Ligands
    Authors: 李立偉,;Lee,Li-Wei
    Contributors: 材料科學與工程研究所
    Keywords: 金屬有機配位聚合物;Metal–organic frameworks;Homochiral;Nanotube;Pillared-layer;Self-assembly
    Date: 2016-05-03
    Issue Date: 2016-06-04 12:49:08 (UTC+8)
    Publisher: 國立中央大學
    Abstract: 本論文旨為多孔性金屬有機配位聚合物之設計合成、結構分析與性質研究。過渡金屬鹽類與中性含吡啶配基或雙羧酸根配基以自組裝法合成出11個多孔有機金屬配位聚合物,產物結構皆經由紅外線共振光譜、元素分析、熱重分析、單晶X光繞射分析與粉末X光粉末繞射分析等方法鑑定。合成之多孔金屬有機配位聚合物結構多樣,包含一維結構、二維平面結構與三維立體結構。化合物{[Zn2(azpy)(aip)2]·2DMF}n (1)、{[Zn2(dipytz)(aip)2]·DMF·MeOH}n (2)與{[Zn2(tpim)(aip)2]·2.5DMF·2H2O}n (3)皆為二維雙層柱狀結構。化合物{[Zn2(tpim)2(D-cam)2]·10H2O}n (4)和{[Zn2(tpim)2(L-cam)2]·10H2O}n (5) 為二維手性平面結構。化合物{[Cd2(tpim)4(SO4)(H2O)2]·(SO4)·21H2O}n (6)為二維(6,3)磚狀拓樸平面結構。化合物{[Zn(4-abpt)05(3,4-pydc)]·DMAc·1.5MeOH·0.5H2O}n (7)為三維層柱狀結構。化合物{[Zn(4-pimp)(3,4-pydc)]·2DMAc}n (8)和{[Zn2(tpim)(3,4-pydc)2]·4DMF·4H2O}n (9)分別為手性二維平面結構和三維層柱狀結構。化合物[Zn(tpim)(cis-1,4-chdc)]·3H2O (10)為一維單層奈米管狀結構,而化合物[Zn2(tpim)2(trans-1,4-chdc)2]·6H2O (11)為二維層狀結構。
    ;In this thesis, a series of porous metal–organic framework (MOFs) were synthesized by reacting rigid multi-pyridyl ligands, various dicarboxylate ligands and d10 metal ions (Zn2+ and Cd2+) under mild reaction conditions. The structures of these compounds range from one dimensional single-walled nanotubes, and two dimensional layers to three dimensional networks. The structure of the compounds {[Zn2(azpy)(aip)2]·2DMF}n (1), {[Zn2(dipytz)(aip)2]·DMF·MeOH}n (2), and {[Zn2(tpim)(aip)2]·2.5DMF·2H2O}n (3) assume a two-dimensional pillared-bilayer framework with 1D channels created inside the bilayers. Compounds {[Zn2(tpim)2(D-cam)2]·10H2O}n (4) and {[Zn2(tpim)2(L-cam)2]·10H2O}n (5) are composed of homochrial two-dimensional layers with a rectangle-like (4,4) topology. Compound {[Cd2(tpim)4(SO4)(H2O)2]·(SO4)·21H2O}n (6) shows a two-dimensional layer structure with a brick-wall-type (6,3) topology. Compound {[Zn(4-abpt)0.5(3,4-pydc)]·DMAc·1.5MeOH·0.5H2O}n (7) features a three-dimensional pillared-layer framework with a (3,4)-connected net. Compound {[Zn(4-pimp)(3,4-pydc)]·2DMAc}n (8) adopts a homochiral two-dimensional layered structure and {[Zn2(tpim)(3,4-pydc)2]·4DMF·4H2O}n (9) displays a homochiral three-dimensional pillared-layer network. Compound [Zn(tpim)(cis-1,4-chdc)]·3H2O (10) displays an independent 1D single-walled metal–organic nanotube and [Zn2(tpim)2(trans-1,4-chdc)2]·6H2O (11) shows a two-dimensional layered structure.
    All of the compounds are porous materials with different pore volumes and channel shapes. The pillared-bilayer frameworks of 1–3 have different pore volumes and channel shapes depending on the length and shape of the pillar ligands as well being feasible to tune the structural flexibility (1 and 2) or rigidity (3) through solvent-exchange processes. The resoluting MOFs exhibit a higher selective adsorption of CO2 over H2 and N2. It is noteworthy that the enantiopure compounds 4 and 5 showed an uncommon gate-opening effect on CO2 sorption and displayed a wide hysteresis loop upon desorption under ambient conditions. Compound 6 consists of a 2D layer structure with two types of sulfate anions and exhibits anion exchange capability with SCN− or N3− anions. Interestingly, the anion-exchanged products of 6 with SCN− or N3− are very different. Compound 7 adopted a three-dimensional porous pillared-layer framework with 1D honeycomb channels. Remarkably, the tetrahedral coordination environment of ZnII ions in 7 could be changed by the presence of other transition metal ions in a DMAc solution. Furthermore, compound 7 also displayed significant non-linear optical behavior. Compounds 8 and 9 crystallize in the homochiral orthorhombic space group P212121. Compound 8 adopted a 2D layer structure. Compound 9 showed a 3D pillared-layer framework with the rectangular-shape one-dimensional channels and revealed significant reversible the thermochromic behavior. Compounds 10 and 11 were constructed from the conformationally flexible 1,4-H2chdc (cis- or trans-) and tpim ligands under hydrothermal conditions and displayed different gas adsorption behaviors.
    Appears in Collections:[材料科學與工程研究所 ] 博碩士論文

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