Controllable Synthesis And Electrocatalytic Applications Of Several Coordination Polymers Based On Aromatic Carboxylate

Coordination polymers（CPs）have emerged as novel multifunctionalmaterials benefiting from their high specific surface area, diversestructural topologies, and the wide potential applications in a variety offields including ion exchange, gas adsorption/separation, molecularrecognition, catalysis, optic, electronic, and magnetic materials.Currently, there still are much drawbacks associated withcoordination polymers that limited their applications, such as rationaldesign of functionalities, controllable synthesis, and themicro/nano-polymer stabilities. With the aim of developing newfunctional materials by taking the advantages of coordination polymers,we here developed controllable syntheses of CPs, and investigated theseveral reported metal-organic frameworks （MOFs） for electrochemicalapplications. We further investigate the relationships between theproperties and the compositions, microstructures of MOFs.Three parts are included as following in this thesis:1. We reported the first application of MOFs based on1,3,5-benzenetricarboxylic acid （H3BTC） as electro-catalysts for O₂reduction. We found that stable [Cu2（OH）（2,2′-bipy）2（BTC）·2H2O]n（Cu-bipy-BTC） exhibits excellent and catalytic activity towards4e-reduction of O₂. Though the mechanism of Cu-bipy-BTC catalyzed O₂reduction is unknown yet, the results here provide an alternative toplatinum based electro-catalysts for O₂reduction and extend theelectrochemical application of functional MOFs.2. An amine modified MOF, Al-MIL-53-NH2, namely aluminumaminoterephthalate Al（OH）[H2N-BDC]·0.3（H2N-H2BDC （denoted asMIL-53-NH2））, was designed to modify electrodes for electrochemicaldetection of TNT. As an electron-deficient species, TNT can form aMeisenheimer complex with electron-rich aliphatic amines. The high surface area of MOF and the donor-acceptor interaction betweenAl-MIL-53-NH2and TNT enabled a high sensitive assay of TNT withdetection limit as low as160nM.3. By self-assembling zinc ions and2,6-bis[（4-carboxyanilino）-carbonyl]pyridine, we synthesized fluorescent coordination polymer （CP）with controllable morphologies. We found that the morphologies of CPcould be controlled by the addition of acetic acid or other bridgingligands. Meanwhile, the mechanisms of the structure controllablesynthesis of CP were investigated. Our results indicated that thecompositions and morphologies of the CP are dictated by ligandstructures, coordination modes of metal ions, and the amount of bridgingligands during the synthesis process.