Porous Metal Organic Framework Materials:Synthesis And Sensing, Separation, Proton Conduction And Catalytic Properties

Metal-Organic Frameworks ?MOFs? has arising as novel inorganic-organic hybrid crystalline materials recent years. Compare to traditional porous materials, MOFs have many advantages over mild reaction conditions, well ordered structure and tailorable functionality. These advantages endow MOFs materials with great potential in many areas, including gas storage and separation, sensor, proton conduct, catalysis and drug delivery. With the rapid development of MOFs research, thousands of MOFs materials have been synthesized and focus begin to transform from structure to properties. Meanwhile, a new way has been found when MOFs materials focus on multi-disciplinary crossing research. Although MOFs materials have exhibited many incomparable properties, making the best of the advantages of MOFs materials is still a challenge.In this dissertation, we use some common organic ligands and metal ions to design and synthesize five kinds of metal-organic framework. Based on the d10 metal ions and the carboxylate ligand with aromatic ? rings, we constructed novel MOFs materials for sensing small molecules. Besides, introducing polyoxometalate ?POM? into the MOFs materials endow MOFs with brand-new properties, such as proton conduct, separation and catalysis. Using the mixture ligands methods, tetrazole was introduced into the MOFs by a bridge mode with its two other nitrogen atoms exposed, which can selectively detect metal ions. From the function of ligands, we successfully introduce carbon-carbon double bond into a mesoporous MOFs, which exhibited single crystal to single crystal transformation under UV radiation. In addition, the Ag metal nanoparticle was formed in situ and the composite can catalyze terminal alkyne to react with CO₂ to form acetylenic acid.1) We obtained a luminescent anionic MOFs based on the on the d10 metal ions and the carboxylate ligand with aromatic ? rings via solvothermal method. The obtained compound exhibited well stabilities and selective detection of nitro explosives. Besides, the compound showed moderate C0₂ adsorption. [?CH₃?₂NH₂][Zn₄Na?BPTC?₃]·4CH₃OH·2DMF?1? BPTC= biphenyl-3,3',5,5'-tetracarboxylic acid2) A POM-encapsulating metal azolate framework has been synthesized by a SAC method. This porous POM-MOF composite shows excellent thermal and chemical stability and our initial results in the purification of ethanol and proton-conducting provide a glimpse into the potential of this material in separation and energy chemistry. [Zn₁₂?trz?₂₀][SiW₁₂O₄₀]·₁1H₂O ?2? trz= 1,2,4-triazole3) A new POM-pillared metal organic framework has been successfully prepared by hydrothermal method. Owing to the hydrophily and redox properties of POM, the obtained MOFs materials exhibited proton-conducting properties as well as intrinsic peroxidase-like activity for colorimetric assay of H₂O₂. Cu₆?trz?₁₀?H₂O?4[H₂SiW₁₂O₄₀]·8H₂O ?3? trz= 1,2,4-triazole4) Adopting a mixture ligands strategy, a new chain based 3D metal organic framework with bbf topology has been constructed. Owing to the existence of uncoordinated nitrogen sites, compound 1 exhibits a turn-off luminescent sensing for Cu2+ ions. Besides, compound 1 could absorb similar amount of Ln3+ions and manifests a selective sensitizer of different Ln3+ ions. [Zn?BPTC?0.5?Tz?]·DMF·CH₃OH ?4?, BPTC=biphenyl-3,3',5,5'-tetracarboxylic acid Tz= tetrazolate5) From the function of ligands, we successfully introduce carbon-carbon double bond into a mesoporous MOFs by solvothermal method. In 5, the carbon-carbon double bond is parallel to each other and the distance between them is below 4.2 A, which satisfy the Schmidt criterion. Thus 5 exhibited single crystal to single crystal transformation under UV radiation. In addition,5 can encapsulate a luminescent dye into the pores of 5 to obtain the dual-emitting dye@mesoMOF composite. And the obtained dye@mesoMOF platform can be utilized to detect a range of volatile aromatic molecule in the vapor state based on two emissions of host and guest. In addition, the Ag metal nanoparticle was formed in situ and the composite can catalyze terminal alkyne to react with C0₂ to form acetylenic acid. Zn₄?OH?₄?BTB?_4/3?bpe?₂·9CH₃OH·17DMF ?5? H₃BTB=1,3,5-tris?4-carboxyphenyl?benzene bpe=1,2-di?4-pyridyl?ethylene...