A Study On Synthesis,Structure And The Properties Of Tetracarboxylic Acid Coordination Polymer Materials

In recent years,with the increase of people?s awareness of environmental protection,water pollution has attracted great attention.The toxicity and carcinogenicity of organic dyes and metal ions in water pollution sources are also becoming a huge threat to human life and other biological species.Therefore,it is particularly important to develop a sensor that detects metal ions and a material that has photocatalytic degradation of organic pollutants.In this paper,three tetracarboxylic acid organic ligands were used,and 12 kinds of coordination polymer materials were synthesized under hydrothermal or solvothermal conditions with different nitrogen-containing auxiliary ligands and transition metal ions:[Co?L1?0.5?1,4-bib??H2O?3]n?1?,[Ni?L1?0.5?1,4-bib??H2O?3]n?2?,[Zn3?L1?2?COOH?8?1,4-bib??H2O?2]n?3?,[Cd?H2L1??4,4?-bip?]n?4?,{[Ni4?L2?2?1,4-bib?3?H2O?8]·4H2O}n?5?,[Co5?L2?2??3-OH?2?H2O?8]n?6?,[Co2?L2??4,4?-bip??H2O?3]n?7?,{[Co2?L2-COOH??phen?2]H2O)}n?8?,[Co?L3?0.5?1,4-bib?]n?9?,{[Zn?H2L3??1,2-bimb?]·2H2O}n?10?,[Cd?L3?0.5?1,4-bimb?]n?11?,[Zn?L3?0.5?1,4-bib?]n?12?,H4L1=1,4-di?2,6-dimethyl-3,5-dicarboxypyridyl?benzene,H4L2=1-?3,5-dicarboxy benzyl?-3,5-pyrazole dicarboxylic acid,H4L3=5-?3,5-dicarboxy benzyloxy?isophthalic acid,1,4-bib=1,4-bis?1-imidazol-yl?benzene,4,4?-bimb=4,4?-bis?imidazole-1-ylmethyl?biphenyl,4,4?-bip=4,4?-bis-?imidazole-1-yl?biphenyl,phen=1,10-Phenanthroline,1,2-bimb=1,2-bis??1-imidazolyl?methyl?benzene,1,4-bimb=1,4-bis??1-imidazolyl?methyl?benzene.The synthesis method of materials was discussed;The structure of the materials was described;The fluorescence and photocatalytic degradation properties of the materials were tested experimentally.The magnetic properties of some materials and the effect of detecting metal ions as fluorescent probes were studied.The main research contents of the thesis are as follows:1.The main ligand of organic carboxylic acid H₄L₁,nitrogen-containing auxiliary ligands 4,4?-bip and 1,4-bib were employed to react with transition metals Co,Ni and Cd,coordination polymer materials 1-4 were successfully synthesized in hydrothermal or solvent heat.1 and 2 are heterogeneous 1D chain structures,while 3 and 4 are 2D planar structures;photocatalytic degradation of methylene blue shows that the degradation activity sequence is 1>4>2>3;magnetic studies indicate that 1 and 2 both antiferromagnetic properties.2.The main ligand of organic carboxylic acid H₄L₂,nitrogen-containing auxiliary ligands,4-bib,4,4?-bip,4,4?-bimp and phen were employed to react with transition metals Co and Ni,coordination polymer materials 5-8 were successfully synthesized under hydrothermal conditions.5-7 are 3D framework,and 8 is a 1D chain formed by hydrogen bondings;Photocatalytic degradation of methylene blue exhibits that the degradation activity sequence is 5>7>6>8;magnetic studies indicate that:5-8 are antiferromagnetic.3.The main ligand of organic carboxylic acid H₄L₃,nitrogen-containing auxiliary ligands,1,4-bib,1,2-bimb and 1,4-bimb were employed to react with transition metals Co,Zn and Cd,coordination polymer materials 9-12 were successfully synthesized under hydrothermal conditions.9 and 10 generate a 2-fold interpenetrating architecture,11displays a 4-fold interpenetrating architecture,while 12 is 3D framework.Fluorescence probe experiments show that 10,11 and 12 can be in the form of fluorescence quenching.The detection limits of Fe³⁺were 2.33??,0.92??,1.03??,respectively.The photocatalytic degradation of methylene blue showed that the degradation activity sequence was 12>10>9>11;magnetic studies showed that 9 showed antiferromagnetic properties.