Synthesis And Properties Of New-type Molecule-based Metal-organic Framework Materials

As a kind of new crystalline material, metal-organic frameworks?MOFs? have some attractive advantages of larger pore size, higher specific surface areas and various structures, which have great potential in various applications such as gas storage and separation, catalysis, chiral separation, drug delivery, molecular recognition and fluorescence properties. Thus far, the reported MOFs are in unvanquishable number, but the synthesis of stable MOFs with unique properties is still a great challenge, especially for the supramolecular isomers and stable Zr-MOFs. Acoording to the crystal engineering principle and experience, we have successfully constructed a series of new MOFs materials. Based on the detailed structural characterization, we studied their gas adsorption properties and the relationship between structures and properities.Chapter 1: we briefly introduced the current development of metal-organic frameworks materials, their structural characteristics and application fields and so on. At last, we mainly clarify the basis and significance of the topics we choose.Chapter 2: Reaction with Co²⁺ ions and the flexible tricarboxylate ligand triggered by reaction solvents, a pair of supramolecular isomers of 3D Co-MOFs?470-MOF and 471-MOF? were synthesized. Furthermore, we analysed the structural differences based on the conformational changes of the ligands and secondary building units, which lead to their different adsorption behaviours.Chapter 3: With the use of our pore regulating strategy, we successfully constructed three 3D Zr-MOFs?493-MOF-BA, 493-MOF-NA and 493-MOF-TATB? with different N-rich pore wall by adjusting the terminal group point to the pore. Gas adsorption experiments show that the high N-rich pore wall resulted in Zr-MOFs with improvement of CO₂ gas uptake.Chapter 4: We firstly constructed and reported three-dimensional Zr-MOFs?509-MOF and 514-MOF? with the topology by use of two tricarboxylate ligands with different flexibility. 509-MOF has the 2-fold interpenetrating structure with microporous nano cages. Meanwhile, the non-interpenetrating structure of 514-MOF include microporous cages and one-dimensional mesoporous channels. Both MOFs show good behavior for energy gas adsorption and the separation of CO₂ in mixture gases.