| Nano-porous metal-organic framework is the coordination polymer with intriguing structural motifs which can be self-assembled by transition metal ions and multi-dental organic ligands containing oxygen and nitrogen. For its adjustable pore size, ordered pore structure, hige specific surface area, functional pore environment and unique characteristics as photonics, electrochemistry and magnetism, which can be potential applications in gas adsorptive separation and storage, molecular magnet, catalysis, photoelectric material. However, with the limitation of pore size and pore structure, most application of metal-organic framework is not fully utilized. Thus, it is a great challenge to search for a simple and effect way to synthesis metal-organic framework with adjustable pore size and ordered pore structure.MOFs can be designed more excellent performance through functional design after the modification synthesis and loading active substances based on existing properties, which can also be extend application field of MOFs. The main content of this dissertation are as follows:1. Based on AHU-1, which can be successfully formed mesostructured MOFs in which mesopore walls are constructed from microporous Cu3(BTC)2, in joining the different anionic surfactant or sulphonate. According to the experiment results from BET and TEM, These mesostructured MOFs of Cu3(BTC)2 possess a mesopore system with tunable diameters from 4.8nm of AHU-1 to 8.8 nm of sample 1,12.4nm of sample 3,14.7nm of sample 4,18.4nm of sample 5, with adjustable pore size and ordered mesoporous structure. Campared sample 1 with sample 2, it can be seen that adding different molar ratio of anionic surfactant has no obvious effect on the size of pore diameters. The Methylene Blue adsorption experiments show that sample 1 with mesostructured is much quick than HKUST-1 which only contains micropore, for the Methylene Blue molecules are larger than the diameters of HKUST-1 so as to restrict the adsorption and diffusion. While, sample 1 with 8.8nm mesostructured are larger than Methylene Blue molecules and better for diffusion and absorption, thus the adsorption property of which to Methylene Blue are better than HKUST-1. 2. Make use of the MOF of Cu3(BTC)2, every copper ions has two unsaturated metal-binding sites, by introducing mercaptan that can make the unsaturated metal site of copper ions react with it and form solid copper sulphur keys. In the solution of anhydrous toluene, Cu3(BTC)2 react with 1-Octanethiol and dodecyl mercaptan under stirring at normal temperature and pressure can synthesized Cu3(BTC)2 which postsynthetic modification by mercaptan, experiment result show that this method is simple and effect. The MOF of Cu3(BTC)2 PSM by mercaptan is partial modification without internal change in framework, which covered by a long alkyl chain and have a favorable hydrophobicity. Properties research shows that hydrophobic modified Cu3(BTC)2 has a high and favorite absorption to hydrophobic dyes as methyl red, while not adsorb methylene blue, through which shows an preferential adsorption purpose to different dyes.3. In the solution of anhydrous toluene, the mixture of MIL-101 and ethylenediamine was stirred with heationg to reliux. The ethylenediamine of modified MIL-101, one amine group is linked to a CUS of chromium of MIL-101 by direct ligation, the other amine group can easy reaction with metal ion, and fixed it into the cage of MIL-101, washed with de-ionized water and ethanol, which can remove metal ion on the surface of MIL-101 or those are not react with ethylenediamine. It can be guarantee the sulfide which produce by H2S and metal ions in the cage of MIL-101, According to the experiment results from TEM, the size of generated sulfide is between lOnm that are equal to the cage diameter of MOFs MIL-101. The fluorescence of sulfide loading in MIL-101, inspire and launch light happen mobile due to influence of framework structure. |
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