The Novel Porous Materials Containing Carboxylic And Azole Groups And Their Properties

Porous Coordination Polymers (PCPs), called also as Metal Organic Frameworks (MOFs) are a kind of new porous crystalline materials, and the infinite network constructed by the self-assembly of metal ion (clusters) and organic ligands. As novel functional porous materials, MOFs have been promising materials for gas storage and separation, catalysis, magnetism, luminescence, molecular recognition, medicine, etc due to their high specific surface area, tunable pore size and finely functionalization. Therefore the wide attentions have been paid to the synthesis and properties of MOF materials.In this thesis, some carboxylic acid, such as H2TBA, H2BDC and H4abtc, and triazole (Hdmtrz) were selected as ligands, and self-assembled into a new type of porous materials with Znic Azolate Carboxylate framework by solvothermal process. Some interesting properties such as fluorescence response and adsorption properties were investigated. The results were divided into five parts as following:In part one, we fully reviewed the basic concept, history, basic classification, possible compositionts and synthetic techniques of MOFs, and we also summurized some properties and application of MOFs, such as gas storage and separation, catalysis, magnetism, luminescence, molecular recognition, medicine etc. Based on the above-mentioned reviews, some research aim and topics of this thesis were given in this part.In part two, three microporous materials with anion frameworks, MAC-3, MAC-12, MAC-12’, were prepared by the solvothermal treatment of Zinc salts and mixed ligands containing some carboxylic ligands (H2TBA or H2BDC) and 3, 5-dimethyl-1H-1,2,4-triazole (Hdmtrz). MAC-12 and MAC-12’pocesses an interesting property of reversible phase transition at the irratation of temperature (heating at 90 ℃) and (dichloromethane), called breathing effect. MAC-12 and MAC-12’ may be an ideal sensor pairs to some particular solvents by their specific fluorescent properties.In part three, MAC-12’as an anion framework, was observed as a cation dye absorber such as RB and MB, MAC-12’ can absorb 88% RB and 70% MB, respectively, in 0.05 mM dye solution. The findings that, in the RB/SD mixed solution MAC-12’can slectively absorb RB, shows the dye absorption of MAC-12’is a cation exchange process. The bleaching experiments in the sodium salt solution further demonstrated that the dye adsorption of MAC-12’ is reversible.In part four, a 3-dimensional interconnecting porous MOF material, named as Zn-abtc-dmtrz, was synthesized in the solvothermal condition by using H4abtc and Hdmtrz as the mixed ligands. The adsorption ability of CO2, N2, H2 for Zn-abtc-dmtrz has been evalutated. The results have showed that this material holds good selective adsorption ability of CO2 over N2 and O2. The structure has a high CO2 adsorption capacity and low CO2 adsorption enthalpy.In the last part, some important results have been summarized, for example, some compounds obtained and the specific properties observed.