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Based On 5 - Phosphonic Acid -1,3 - Phthalate Coordination Polymer Synthesis, Characterization And Performance

Posted on:2011-09-12Degree:MasterType:Thesis
Country:ChinaCandidate:T B LiaoFull Text:PDF
GTID:2191360305497078Subject:Inorganic Chemistry
Abstract/Summary:PDF Full Text Request
Metal-organic frameworks (MOFs) are a kind of compounds with periodic network structure which are constructed by small organic ligands and metal ions or clusters through self-assemble process. Comparing with traditional inorganic frameworks, the structure of MOFs is more controllable, and the synthesis of which is processed under milder condition. Numerous novel MOFs have been obtained by adjusting metal to ligand ratio, solvents, templates and/or synthesis methods directed by crystal engineering. However, there are still great challenges in this new research field.Herein,15 new MOFs based on 5-phosphonobenzene-1,3-dicarboxylic acid was solvothermal synthesized and characterized by X-ray single-crystal diffraction, elemental analysis (EA), infrared spectroscopy (IR) and thermogravimetric analysis (TGA). The crystalline phase purity was independently confirmed by powder X-ray diffraction. The property study such as catalysis, gas storage was carried out on some of the novel MOFs. This thesis is divided into three parts:(1) Two MOFs based on similar trinuclear secondary building unit have been synthesized by using mixed-solvothermal and layered-solvothermal method, respectively. Two MOFs possess different topology, which could be caused by the presence of one coordination water in ZnPC-1. ZnPC-2 is a porous structure which shows excellent adsorption and catalysis ability. Additionally, ZnPC-2 is a typical 3rd generation MOF showing "shrink-swell" behavior. Based on single X-ray diffraction result, a proton transfer should be occurred in ZnPC-2 during the "shrink-swell" behavior.(2) Eight new MOFs were obtained through adjusting amines or meta to ligand ratio. By using different amines, six MOFs have been obtained. The role of the amines is greatly different in directing the structure-assembly. In ZnPC-3 and ZnPC-4, amines coordinate to metal ions; in ZnPC-5 to ZnPC-8, amines exist in pores serving as templates. ZnPC-7 and ZnPC-8 are "amine decorated ZnPC-2", which disclose enhanced CO2 adsorption ability. Through changing the metal-to-ligand ratio, another two MOFs have been obtained.(3) A series of allomers were synthesized based on Cu(Ⅱ)/Mn(Ⅱ)/Ni(Ⅱ)/Mg(Ⅱ), named as CuPC-1, MnPC-1, NiPC-1, MgPC-1 respectively. In addition, with the same procedure to that of ZnPC-9 and replacing Zn(Ⅱ) ion with Co(Ⅱ), a novel allomers-structure, named CoPC-1 was isolated, which shows antiferromagnetic coupling in the temperature of 25-300K.
Keywords/Search Tags:Coordination polymer, phosphonic acid, crystal structre, catalysis, sorption
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