吡啶羧酸雜合配體MOFs材料的組裝及吸附性能研究
發(fā)布時間：2018-07-25 19:50
【摘要】：金屬有機骨架化合物(Metal-Organic Frameworks,簡稱:MOFs),以其高的比表面積、豐富多樣的結(jié)構(gòu)以及可功能化修飾的孔道受到了人們的廣泛關(guān)注。通過合理地設(shè)計有機配體并采用適當?shù)慕饘僭纯梢灾苽渚哂蓄A(yù)期結(jié)構(gòu)的MOFs材料并實現(xiàn)其結(jié)構(gòu)的功能化。MOFs材料作為一種新型功能化多孔材料,在氣體吸附與分離、質(zhì)子傳導(dǎo)、藥物緩釋、傳感、催化以及光電磁等領(lǐng)域均展現(xiàn)出了潛在的應(yīng)用價值。近年來,由于MOFs材料具有高比表面積以及低密度等特點,其在氣體吸附與分離應(yīng)用方面展示出了巨大的優(yōu)勢。通過在結(jié)構(gòu)中引入開放的金屬位點、路易斯堿活性位點或形成穿插結(jié)構(gòu)可以顯著提高MOFs材料的氣體吸附與分離性能。這種結(jié)構(gòu)和功能的可調(diào)控性使MOFs材料在二氧化碳捕捉、氣體存儲以及天然氣純化等方面具有重要的實際應(yīng)用價值。因此,本論文主要圍繞MOFs材料在氣體吸附與分離方面的應(yīng)用展開了一系列研究工作。本論文選用兩個吡啶羧酸類有機物3,5-二(4’-羧基苯基)吡啶(H_2BCPPy)和2,6-二(3’,5’-二羧基苯基)吡啶(H_4BDCPPy)作為配體,利用次級結(jié)構(gòu)基元法以及超分子構(gòu)筑塊法與不同種類的金屬源構(gòu)筑了11個結(jié)構(gòu)新穎的MOFs材料,對所合成的化合物進行了結(jié)構(gòu)解析、性質(zhì)表征及性能測試,并深入探究了這一系列MOFs材料在氣體吸附與分離、碘的吸附與釋放及有機染料的吸附與分離等方面的應(yīng)用。本論文的研究成果主要包含以下三個方面:(1)以吡啶二齒羧酸H_2BCPPy為有機配體,與含有不同陰離子的金屬銅源通過自組裝法制備了五個結(jié)構(gòu)新穎的MOFs材料1-5。其中,化合物1和2均采用硝酸銅為金屬源,通過改變反應(yīng)溶劑的種類得到了兩個結(jié)構(gòu)新穎的化合物,兩個化合物的結(jié)構(gòu)中均具有經(jīng)典的輪槳狀雙核銅無機次級結(jié)構(gòu)基元。化合物3和4均是以碘化亞銅為金屬源制備的MOFs材料。將碘離子引入到反應(yīng)體系中,通過改變金屬源與有機配體的比例得到了兩個結(jié)構(gòu)不同的化合物,其結(jié)構(gòu)中均具有經(jīng)典輪槳狀雙核銅以及多核Cu4I4金屬簇兩種無機次級結(jié)構(gòu)基元�；衔�3的比表面積大于其他已報道的基于Cu4I4金屬簇的MOFs材料,而且它對一些小分子氣體具有很好的吸附能力,并能高效分離氧氣和氮氣、丙烷和甲烷。化合物4所具有的超高孔隙率(78.2%)使其表現(xiàn)出優(yōu)異的碘吸附與釋放能力。化合物5是以硫酸銅為金屬源制備的MOFs材料。將硫酸根離子引入反應(yīng)體系中,得到了同時具有經(jīng)典輪槳狀雙核銅以及少見的六核硫酸銅簇兩種無機次級結(jié)構(gòu)基元的結(jié)構(gòu)�；衔�5的陰離子骨架結(jié)構(gòu)及空曠的孔體積使其能夠快速吸附陽離子有機小分子染料(亞甲基藍、甲基紫、羅丹明B)以及中性染料(中性紅),但是不吸附陰離子染料(甲基橙和金橙II)。此外,化合物5能夠快速從等摩爾混合染料甲基橙亞甲基藍和金橙II亞甲基藍中選擇性吸附陽離子染料亞甲基藍。(2)以吡啶二齒羧酸H_2BCPPy為有機配體,與不同的金屬源構(gòu)筑了四個具有高穩(wěn)定性的MOFs材料6-9。其中化合物6和7為同構(gòu)的化合物�；衔�6的結(jié)構(gòu)中包含較少報道的九連接三核金屬銦簇無機次級結(jié)構(gòu)基元,因此,化合物6不僅具有較好的熱穩(wěn)定性能,而且能夠在水蒸氣中較為穩(wěn)定地存在�；衔�6對二氧化碳展現(xiàn)出很好的捕獲能力,在常壓273和195 K條件下對二氧化碳的最大吸附量為129和400 cm3 g-1。此外,化合物6對氧氣和氮氣、二氧化碳、乙烷、丙烷和甲烷有很好的分離能力。通過改變合成化合物7時反應(yīng)溶劑的種類,得到了另一種具有無限金屬錳鏈的二維層狀的化合物8,在該化合物的結(jié)構(gòu)中,有機配體表現(xiàn)出較強的天線效應(yīng),對金屬錳的熒光有明顯的增強效果�；衔�9是以硝酸鎘為金屬源構(gòu)筑的具有無限金屬鎘鏈的MOFs材料,其結(jié)構(gòu)中獨特的3.5?超微孔孔道使其對二氧化碳和氮氣具有很好的篩分效應(yīng)。(3)以吡啶四齒羧酸H_4BDCPPy為有機配體,利用超分子構(gòu)筑塊法與兩種金屬源制備了兩個具有不同金屬有機多面體籠的MOFs材料10-11。這兩種化合物的結(jié)構(gòu)中都具有較少報道的線型四核金屬簇。其中化合物10具有較高的比表面積,且對一些小分子氣體具有很好的吸附能力,并能高效地分離丙烷和甲烷�；衔�11結(jié)構(gòu)中具有少見的48高連接數(shù)金屬有機多面體籠。本論文中,利用次級結(jié)構(gòu)基元法及超分子構(gòu)筑塊法,采用兩種吡啶羧酸類配體與不同的金屬源構(gòu)筑了11個結(jié)構(gòu)新穎的MOFs材料。利用MOFs材料結(jié)構(gòu)中的多孔性,通過分析不同材料各自的結(jié)構(gòu)特點,將實驗與理論模擬相結(jié)合,探究了這些材料在小分子氣體的吸附與分離、碘吸附與釋放以及有機染料的吸附與分離方面的應(yīng)用前景。
[Abstract]:Metal-Organic Frameworks (MOFs) has attracted wide attention for its high specific surface area, rich diversity of structures and functional modified pores. By rational design of organic ligands and appropriate metal sources, the expected structure of MOFs materials can be prepared and their structure can be realized. Functional.MOFs material, as a new functional porous material, has shown potential application value in the fields of gas adsorption and separation, proton conduction, drug release, sensing, catalysis and photoelectricity. In recent years, because of the high specific surface area and low density of MOFs, it has been used in the application of gas adsorption and separation. By introducing open metal sites in the structure, the Lewis base active site or interspersed structure can significantly improve the gas adsorption and separation performance of the MOFs material. This structure and function can make MOFs materials in carbon dioxide capture, gas storage, and natural gas purification. Therefore, this thesis focuses on the application of MOFs materials in the application of gas adsorption and separation. This paper uses two pyridine carboxylic acids, 3,5- two (4 '- carboxy phenyl) pyridine (H_2BCPPy) and 2,6- two (3', 5 '- two carboxy phenyl) pyridine (H_4BDCPPy) as a ligand. 11 novel MOFs materials were constructed by the hierarchical element method, supramolecular block method and different kinds of metal sources. The structural analysis, characterization and performance testing of the synthesized compounds were carried out. The adsorption and separation of gas, adsorption and release of iodine and adsorption of organic dyes on this series of MOFs materials were deeply explored. The research results of this paper mainly include the following three aspects: (1) five novel structural MOFs materials, 1-5., are prepared by self assembly by using H_2BCPPy as the organic ligand with pyridine two tooth carboxylic acid as the organic ligand, and the compounds 1 and 2 use copper nitrate as the metal source by changing the reaction. Two novel compounds were obtained, and the structure of the two compounds had the classical round paddle double nuclear copper inorganic secondary structural elements. The compounds 3 and 4 were MOFs materials prepared with copper iodide as the metal source. The iodide ion was introduced into the reaction system, and the ratio of the metal and organic ligands was changed. Two compounds with different structures are composed of two kinds of inorganic secondary structure elements, classical wheel propeller double nucleus copper and multi nucleus Cu4I4 metal cluster. The specific surface area of compound 3 is larger than that of other reported MOFs materials based on Cu4I4 metal clusters, and it has good adsorption capacity for some small molecule gas bodies and can be separated efficiently. Oxygen and nitrogen, propane and methane. The super high porosity (78.2%) of compound 4 shows excellent iodine adsorption and release ability. Compound 5 is a MOFs material prepared with copper sulfate as the metal source. The sulfate ion is introduced into the reaction system, and it has a canonical paddle double nucleated copper and a rare six nuclear copper sulfate. The structure of two inorganic secondary structural elements. Compound 5's anionic skeleton structure and open pore volume enable it to quickly adsorb cationic organic small molecular dyes (Ya Jiaji blue, methyl violet, Luo Danming B) and neutral dyes (neutral red), but no anion dye (methyl orange and gold orange II). In addition, compound 5 can be fast. The selective adsorption of cationic dye methylene blue from methyl orange methylene blue and gold orange II methylene blue. (2) with pyridine two tooth carboxylic acid H_2BCPPy as organic ligand, four compounds with high stability, 6-9., compound 6 and 7, are constructed with different metal sources. Compound 6 structure Containing less reported nine connection three nuclear metal indium inorganic secondary structural elements, therefore, compound 6 not only has good thermal stability, but also can be more stable in water vapor. Compound 6 shows a good capture capacity for carbon dioxide, and the maximum adsorption capacity of carbon dioxide to carbon dioxide under the condition of 273 and 195 K is 12. 9 and 400 cm3 g-1. in addition, compound 6 has a good separation capacity for oxygen and nitrogen, carbon dioxide, ethane, propane, and methane. By changing the kind of reaction solvent of synthetic compound 7, another two-dimensional layered compound with infinite metal manganese chain is obtained. In the structure of the compound, the organic ligand shows a strong day. Line effect has an obvious enhancement effect on the fluorescence of metal manganese. Compound 9 is a MOFs material with infinite metal cadmium chain constructed with cadmium nitrate as the metal source. The unique 3.5? Ultra micropore channel in its structure makes it have a good screening effect on carbon dioxide and nitrogen. (3) using the pyridine four tooth carboxylic acid as the organic ligand, using superfractionation. Two MOFs materials with different metal organic polyhedron cages with different metal organic polyhedron cages have been prepared by substructure block method and two kinds of metal sources. The structure of the two compounds with different metal organic polyhedron cages have less reported linear four core metal clusters, of which compound 10 has a high specific surface area, and has a good adsorption capacity for some small molecular gases and can be efficiently separated. A rare 48 high junction metal polyhedron cage is rare in the 11 structure of propane and methane. In this paper, 11 novel MOFs materials have been constructed with two kinds of pyridine carboxylic ligands and different metal sources using the secondary structure element method and supramolecular block method. The structure characteristics of different materials are analyzed, and the experimental and theoretical simulation are combined to explore the application prospects of these materials in the adsorption and separation of small molecular gases, the adsorption and release of iodine, and the adsorption and separation of organic dyes.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O641.4;O647.3
本文編號：2144891
[Abstract]:Metal-Organic Frameworks (MOFs) has attracted wide attention for its high specific surface area, rich diversity of structures and functional modified pores. By rational design of organic ligands and appropriate metal sources, the expected structure of MOFs materials can be prepared and their structure can be realized. Functional.MOFs material, as a new functional porous material, has shown potential application value in the fields of gas adsorption and separation, proton conduction, drug release, sensing, catalysis and photoelectricity. In recent years, because of the high specific surface area and low density of MOFs, it has been used in the application of gas adsorption and separation. By introducing open metal sites in the structure, the Lewis base active site or interspersed structure can significantly improve the gas adsorption and separation performance of the MOFs material. This structure and function can make MOFs materials in carbon dioxide capture, gas storage, and natural gas purification. Therefore, this thesis focuses on the application of MOFs materials in the application of gas adsorption and separation. This paper uses two pyridine carboxylic acids, 3,5- two (4 '- carboxy phenyl) pyridine (H_2BCPPy) and 2,6- two (3', 5 '- two carboxy phenyl) pyridine (H_4BDCPPy) as a ligand. 11 novel MOFs materials were constructed by the hierarchical element method, supramolecular block method and different kinds of metal sources. The structural analysis, characterization and performance testing of the synthesized compounds were carried out. The adsorption and separation of gas, adsorption and release of iodine and adsorption of organic dyes on this series of MOFs materials were deeply explored. The research results of this paper mainly include the following three aspects: (1) five novel structural MOFs materials, 1-5., are prepared by self assembly by using H_2BCPPy as the organic ligand with pyridine two tooth carboxylic acid as the organic ligand, and the compounds 1 and 2 use copper nitrate as the metal source by changing the reaction. Two novel compounds were obtained, and the structure of the two compounds had the classical round paddle double nuclear copper inorganic secondary structural elements. The compounds 3 and 4 were MOFs materials prepared with copper iodide as the metal source. The iodide ion was introduced into the reaction system, and the ratio of the metal and organic ligands was changed. Two compounds with different structures are composed of two kinds of inorganic secondary structure elements, classical wheel propeller double nucleus copper and multi nucleus Cu4I4 metal cluster. The specific surface area of compound 3 is larger than that of other reported MOFs materials based on Cu4I4 metal clusters, and it has good adsorption capacity for some small molecule gas bodies and can be separated efficiently. Oxygen and nitrogen, propane and methane. The super high porosity (78.2%) of compound 4 shows excellent iodine adsorption and release ability. Compound 5 is a MOFs material prepared with copper sulfate as the metal source. The sulfate ion is introduced into the reaction system, and it has a canonical paddle double nucleated copper and a rare six nuclear copper sulfate. The structure of two inorganic secondary structural elements. Compound 5's anionic skeleton structure and open pore volume enable it to quickly adsorb cationic organic small molecular dyes (Ya Jiaji blue, methyl violet, Luo Danming B) and neutral dyes (neutral red), but no anion dye (methyl orange and gold orange II). In addition, compound 5 can be fast. The selective adsorption of cationic dye methylene blue from methyl orange methylene blue and gold orange II methylene blue. (2) with pyridine two tooth carboxylic acid H_2BCPPy as organic ligand, four compounds with high stability, 6-9., compound 6 and 7, are constructed with different metal sources. Compound 6 structure Containing less reported nine connection three nuclear metal indium inorganic secondary structural elements, therefore, compound 6 not only has good thermal stability, but also can be more stable in water vapor. Compound 6 shows a good capture capacity for carbon dioxide, and the maximum adsorption capacity of carbon dioxide to carbon dioxide under the condition of 273 and 195 K is 12. 9 and 400 cm3 g-1. in addition, compound 6 has a good separation capacity for oxygen and nitrogen, carbon dioxide, ethane, propane, and methane. By changing the kind of reaction solvent of synthetic compound 7, another two-dimensional layered compound with infinite metal manganese chain is obtained. In the structure of the compound, the organic ligand shows a strong day. Line effect has an obvious enhancement effect on the fluorescence of metal manganese. Compound 9 is a MOFs material with infinite metal cadmium chain constructed with cadmium nitrate as the metal source. The unique 3.5? Ultra micropore channel in its structure makes it have a good screening effect on carbon dioxide and nitrogen. (3) using the pyridine four tooth carboxylic acid as the organic ligand, using superfractionation. Two MOFs materials with different metal organic polyhedron cages with different metal organic polyhedron cages have been prepared by substructure block method and two kinds of metal sources. The structure of the two compounds with different metal organic polyhedron cages have less reported linear four core metal clusters, of which compound 10 has a high specific surface area, and has a good adsorption capacity for some small molecular gases and can be efficiently separated. A rare 48 high junction metal polyhedron cage is rare in the 11 structure of propane and methane. In this paper, 11 novel MOFs materials have been constructed with two kinds of pyridine carboxylic ligands and different metal sources using the secondary structure element method and supramolecular block method. The structure characteristics of different materials are analyzed, and the experimental and theoretical simulation are combined to explore the application prospects of these materials in the adsorption and separation of small molecular gases, the adsorption and release of iodine, and the adsorption and separation of organic dyes.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O641.4;O647.3
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