| Coordination polymer is a kind of material with periodic network structure formed by self-assembly with metal as node,organic ligand as skeleton and coordination bond as link.Through the change of organic ligands and metal centers,self-assembled complex materials with unique structure and excellent performance are formed,which show a broad application prospect in many fields such as gas storage and separation,catalysis,fluorescence sensing,drug delivery,electrocatalysis and so on.In this paper,based on the optimization of organic ligands and metal ions,the experimental conditions were explored,and a series of research work was carried out to design and construct a new coordination polymer material with gas storage and separation and photocatalytic performance.Two nitrogen-containing carboxylic ligands,4,4-bis?imidazolyl?biphenyl?bibp?,1,3-bis?imidazolyl-1-methyl?benzene?biyb?and 4,5'-azobenzene tetracarboxylic acid?H4dda?,were selected,Nine novel coordination polymer materials have been synthesized by solvothermal method,which include 4-bis?imidazolyl?diphenyl ether?bide?,tri[4-?imidazolyl-1-yl?phenyl]amine?tipa?and transition metal ions Co2+,Cd2+,Mn2+.The structures of 9 kinds of coordination polymer materials were determined and characterized,and the gas adsorption separation experiments of 5 kinds of materials and the photocatalytic degradation experiments of 4 kinds of materials on dyeing wastewater were carried out.The main research contents include the following three aspects:?1?Nine new complexes were successfully prepared under solvothermal conditions,and characterized by structure determination,TG,IR and PXRD.?2?The surface products of five kinds of synthetic MOFs materials Co?pysa??H2O??1?,[Co2?pysa?2?H2O?2]·2H2O?2?,Co2?pysa?2·?biyb??3?,[Co2?pysa?2?dipe?]·2H2O?4?and [Co2?pysa?2?bide?]·2H2O?5?were measured,and the adsorption desorption behavior of CO2,CH4,C2H2,C2H4.The enthalpy of adsorption of MOFs?1?for CO2,CH4,C2H2,C2H4 and the separation performance of ideal binary gas mixture CO2/CH4,CO2/C2H2,CO2/C2H4,C2H2/C2H4,C2H2/CH4 and C2H4/CH4 were studied theoretically.?3?The photocatalytic degradation of methylene blue by [Mn?H3dda?2?DMA??H2O?]·?DMA??6?,[Cd2?dda??tipa?]·4H2O?7?,[Cd2?dda??bide?2?H2O?2]·3H2O?8?and Cd2?dda??bibp?2]·2H2O?9?was studied;The results showed that the degradation rate of methylene blue was 34.7%,76.1%,73.5% and 79.3% for 6,7,8 and 9,respectively.The first-order kinetic rate constants were 2.57×10-3,4.88×10-3,5.91×10-3and 7.07×10-3min-1,respectively.Material 9 was optimized,and the influence factors of its photocatalytic activity and its photocatalytic degradation behavior on the simulated samples were further studied.The results showed that the optimal process conditions were: 800 w xenon lamp as the light source,the amount of catalyst was 15 mg,the amount of H2O2?30% by mass?was 0.3 ml and the pH was equal to 10. |
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