Design And Synthesis Of Novel Porous Crystalline Materials For Luminescent Sensor And Batteries

Metal-organic frameworks(MOFs)are a type of crystalline materals with tunable pore diameter and high surface area,which stemed from the coordinating of metal centers/clusters and multidentate organic linkers.On one hand,as ‘ideal host materials',the combination of porosity with guest molecules allows the generation of luminescent-responsive materials from MOFs.On the other hand,the crystalline MOFs can efficiently provide a ?-?* conjugated matrix for the charge transfer and guest molecule trapping.In addition,polyoxometalates(POMs)are anionic nanosized metal oxygen clusters and capable of building various of hyperstable POMOFs materals.POMs can not only form unique stable structure due to its strong coordination ability,but also support a path for fast charge transportation as electron sponge.Therefore,crystalline MOFs and POMOFs can be treated as remarkable candidate for energy materials.The stable crystalline MOFs,MOF derivatives and POMOFs have been obtained on account of energy storage and conversion.The luminescent,electrochemical properties,and the relationships between structures and properties for these materials have been studied.All these studies are based on two purposes,which one is the mechanism of luminescent-response and energy transfer caused by various aromatic hydrocarbon,and another one is to solve the performance and safety problem of batteries by tunning morphology and functional group of these materials.1.A novel luminescent MOF(abbreviated as Cd-BIPN)has been synthesized under solvothermal condition,which based on cadmium and fluorophore-containing tetradentate carboxylate ligand,namely 1,4-bis(3,5-isophthalic acid)naphthalene(H4BIPN).[(CH3)2NH2]2[Cd(L)]·5DMF(1)Cd-BIPN reveals two kinds of channels,namely open channel,and semi-open channel with aromatic rings tentacles.Cd-BIPN could be a chemical sensor for benzene homologs,especially for 1,2,4-Trimethylbenzene(1,2,4-TMB).This is the first example of MOFs materials serving as sensor of 1,2,4-TMB among benzene homologs.2.A novel kaleidoscope-like topology MOF(abbreviated as Zn-TPTC)formed by Zn2+cations and terphenyl-3,3',5,5'-tetracarboxylic acid(H4TPTC)has been successfully synthesized.[(ZnO)1.5(TPTC)]·4DMF(2)Zn-TPTC contains two types of nanocages that exhibit energy transfer properties consistent with encapsulation within PAHs molecules.The energy can transfer from PAHsmolecules with relative long fluorescence lifetimes to Zn-TPTC network.The photoluminescence quenching of TEOA in the presence of the PAHs@Zn-TPTC were examined,and quenching percentage were approximate 97%.3.Cd-BIPN crystalline with channels and other four porous MOFs with cages were obtained for the application of cathode materials in Li-S batteries.Ti8O8(OH)4-(O2C-C6H4-CO2)6(MIL-125)(3)Ti8O8(OH)4-(O2C-C6H3NH2-CO2)6(NH2-MIL-125)(4)MIL-125 porous carbons(MPC)(5)NH2-MIL-125 porous carbons(NMPC)(6)Cd-BIPN possesses a prodigious high loading quantitative value of sulfur(S content-active material: 72 wt%,electrode: 50.4 wt%)in the MOF/sulfur composites.S/Cd-BIPN cathode displays an outstanding specific discharge capacity(1092 mAh g-1at 0.1C)and mentionable cycling stability.S/NMPC cathode,which based on TiO2 and N-doped porous carbons,exhibites an initial specific capacity of 1551.9 mAh g-1(93% of the theoretical capacity of Li-S batteries).In addition,S/NMPC represents the highest capacity retention cathode composite among these materials in Li-S batteries.4.In order to increase the structural complexity of crystalline hybrids,Wells-Dawson POMs were intrdused in the POMOFs system.Compouds 7 and 8 with multi-fold meso-helixes were successfully isolated via self-assembly.[Ag26(Trz)16(OH)4][P2W18O62](7)Na[Ag16(Trz)9(H2O)4][P2W18O62]·H2O(8)The multi-chelate patterns of Wells-Dawson POMs in 8 represents the highest coordination numbers so far.And for the first time,the Wells-Dawson POMs based hybrids 7and 8 are using as anode materials in lithium-ion batteries(LIBs).The initial specific capacities of 7 and 8 are much higher than(NBu4)6[P2W18O62] and commercial graphite as reference anodes.And both of them show good stable performance after 100 cycles.