Synthesis And Properties Of MOFs Materials Based On Three Aryl Polycarboxyl Acids

In this thesis eight aryl ploycarboxylicacid ligands were designed andsynthesized:9-(4-carboxylnaphthyl)-9H-carbazole-3,6-dicarboxylic acid (L1),9-(3,5-dicarboxyphe-nyl)-9H-carbazole-3,6-dicarboxylicacid (L2),1,3,5-tris(4’-carboxy-3’-hydroxyphenyl)benzene (L3),1,3,5-tris(4’-carboxy-3’-hydroxy[1,1’-biphenyl]-4-yl)benzene (L4),1,3,5-tris(4’-carboxy-3’-methoxyphenyl)benzene (L5),1,3,5-tris(4’-carboxy--3’-methoxy[1,1’-biphenyl]-4-yl)benzene (L6),1,2-di(4’-carboxy-3-methoxyphenyl)be-nzene (L7) and9-(4-((4-carboxycyclohexa-2,4-dien-1-yl)(4-carboxyphenyl)ami-no)phenyl)-9H-carbazole-3,6-dicarboxylic acid (L8). These ligands werecharacterized by1HNMRand13C NMR, respectively. Sixof the above ligands are notreported except L3and L5which were synthesized by a new simple method with animproved yield.MOF1and MOF2were obtained by reaction of L1and L2together withIn(NO3)34.5H2Ovia solvothermal method, respectively. MOF3based onreaction ofL3andCo(NO3)26H2Owas made by the two different methods with the differentcrystalsize.The raw crystal data were collected by X-ray single crystal diffraction andresolved by SHELX-97. The purity of bulk sample was examined by PXRD.Thermogravimetric analysis (TGA) was conducted to investigate the thermal stabilityof the complex.Gas adsorption isotherms of N2, CO2and CH4were measured to investigate theporous structure and thegas sorption propertiesof MOF1at273K. The selectiveadsorption behaviors of MOF1toward CO2/N2, CO2/CH4and CH4/N2were alsoinvestigated andthe adsorption selectivities were calculated by Henry Law with thevalue of60.79，4.29and14.18, respectively, which illustrated MOF1had a highlyselective CO2adsorption property. Furthermore, MOF1exhibited high adsorptionproperties to vapors of benzene, cyclohexane and toluene with the largest uptakeamount of178,114,129cm3/g separately. The PXRD peaks of activated sample of MOF2were extremely different from thatof as-synthesized sample, and the adsorption amount of activated sample to CO2,CH4and N2was quiet low at273K, which indicated that the network structure ofMOF2was unstable and would collapsed when removing free solvents in theprogress of activation.C@Co and C@Co3O4were gained through different themolysis process with MOF3as template. The surface area were calculated via Brunauer-Emmett-Teller (BET)theory with value of342.79and180.70m2/g. The potential applications of C@Coand C@Co3O4as thecarbon supercapacitor were also measured through cyclicvoltammetry (CV).