| Recently,the potential applications of complexes with controllable structures,adjustable pore channels and abundant hydrogen bonds in the field of proton conduction and electrochemical sensors have attracted great attention.This dissertation mainly focuses on the following aspects:Firstly,twosimilaracylthiourea-basedcarboxylateligands:2-?3-benzoylthioureido?ethanoicacid?H3BTEA?and2-?3-benzoylthioureido?propionic acid?H3BTPA?to react with Cu?OAc?2,respectively,one 0D cluster[Cu6ICu6II?BTEA?6?H2O?10?DMF?2]?6H2O?DMF=N,N-dimetylformamide??1?and one 2D cluster polymer[Cu6ICu6II?BTPA?6?H2O?10]n?2?have been synthesized under room temperature.The structures were determined with single-crystal X-ray diffraction.Then the two polymers have been characterized by means of IR spectra,elemental analyses and PXRD.In polymer 1,six CuI were coordinated with six S atoms of ligands forming a Cu-S cluster.In the same time,the other six CuII were coordinated with six organic ligands surrounding the Cu-S cluster.The structure of polymer 2 is similar to 1,the basic structural units are connected by ligands forming two-dimensional structure.The differences between the preparations of the two complexes are very small,but they differ quite a bit in structure.This is going to say that the process of preparation has a great influence on the structure of the compounds.In addition,we study the conductivity of these two complexes at different humidities and temperatures.The conductivities of the two complexes at different ammonia concentrations are further studied.After analysis,it is found that the conductivity under water vapor and ammonia vapor are not significantly different,and the conductivity mechanisms of the two complexes are investigated.Secondly,wepreparesevencomplexeswith2-?2-carboxylphenyl?-1H-imidazole-4,5-dicar-boxylicacid?o-CbPhH2IDC?:[M?o-CPhH2IDC??H2O?3]·2H2O[M=Co?3?,Zn?4?],Mn?o-CPhH2IDC??2,2?-bipy??H2O?2?5?,{[Zn?o-CPhH2IDC??2,2?-bipy?]·0.25H2O}n?6?,{[Mn?o-CPhH2IDC??4,4?-bipy?0.5?H2O?2]·3H2O}n?7?,{[Zn5?o-CPhH2IDC?2?o-CPhHIDC?2?2,2?-bipy?5]·5H2O}n?8?,[Ba?o-CPhH2IDC??H2O?4]n?9?.3,4 and 5 are linked by ligands or auxiliary ligands leading to 0D polymers 6,7,8 and 9 are 1D chain.Then these seven polymers have been characterized by IR spectra,elemental analyses and PXRD.All of these polymers contain a large number of water and hydrogen bonds,which lays a good foundation for the study of proton conductivity,so we learn the proton conductivity of these polymers.Firstly,we study the proton conductivity under different RHs.We find that the proton conductivity of 9 is higher than others totally.It can reach1.36×10-33 S?cm-11 for 100?C and 98%RH.Because the complexes 3 and 4 are isomorphous,the conductivities of them are respectively 1.78×10-44 S?cm-11 and 1.68×10-44 S?cm-1,which are similar.The conductivities of other complexes are in the regular level.Moreover,we study the conductivities of those complexes under NH3·H2O vapor.We find that the conductivity can be improved greatly under NH3·H2O vapor,so this also provides ideas for future research.In order to figure out the influence of NH3 vapor on proton conductivity,we study the sensitivity to NH3gas of polymer 9.It is discovered that the electrochemical impedance gas sensor fabricated by 9 is a promising sensor for ammonia at mild temperature and high RHs.In the end,we discuss the conductivity mechanisms of those complexes according to the data of adsorption and activation energy. |
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