Metal Porphyrin Ligand Polymer Film Interface Assembly And Its Application In The Degradation Of Azo Dye

Based on the bottom-up molecular assembly technology, researches on the design and construction of metal loporphyrin coordination polymers have made a great progress over the last couple of decades. The assembly of molecular devices and molecular machines has been developed towards miniaturization, high density and multi-function. In this thesis, the metalloporphyrins with unique structure and properties were selected and used as linkers for the construction of coordination polymer aggregates or nanoscale materials through interfacial coordination reactions. Composition, structure and physico-chemical properties of the as-prepared materials were investigated. The coordination polymer modified substrates were used as a heterogeneous catalyst to catalyze oxidation of organic dyes at room temperature.The thesis consists of three parts. In the first part, a water-soluble porphyrin (MnTMPyP) was used as a multidentate ligand. Through the coordination interaction between Mn(Ⅱ) and PVP (poly(4-vinylpyridine)), a kind of metalloporphyrin-PVP composite polyelectrolyte was synthesized. Then, based on the coordination binding and van der Waals force organized ultrathin films containing metalloporphyrin coordination polymers were constructed. Compared to the condensed molecular aggregates, the present metalloporphyrin-PVP multilayers may have the advantages of better flexibility and stability, easier to be assembled and use as heterogeneous catalysts. Finally, the present coordination polymerggregates were deposited on the substrate surface and used as heterogeneous catalyst for the oxidation of organic dyes.In the second part, we used the LB technique to prepare monoiayers and multilayers of metalloporphyrins at the air-water interface for the understanding of the relationship between molecular structure and their physico-chemical properties in the films. With an interfacial interactions between polyelectrolyte and B(C6H5)4or its coordination reaction with Pd(Ⅱ), stable monolayers of MnTMPyP-PVP were formed at the air-water interface.Then, these monolayers were transferred onto substrate surfaces by the LB method and characterized by using UV-vis absorption spectra, X-ray photoelectron spectra and electrochemical analysis. Surface morphologies of the as-prepaed LB films were characterized by using a scanning electron microscope and atomic force microscope. Finally, it was revealed that the thin films containing manganese porphyrin complexes could be used to catalyze organic reactions.In the third part, we used the zinc porphyrin (ZnTMPyP) as the linker because of its unique optical and electrical properties. The polyelectrolyes containing ZnTMPyP were synthesized through coordination binding of ZnTMPyP and PVP. The obtained zinc porphyrin polyelectrolyte of ZnTMPyP-PVP was assembled alternatively with (poly(styrenesulfonic acid-co-maleic) acid (PSS) based on the electrostatic interaction by the layer-by-layer method. The assembled LBL multilayers were characterized by using UV-vis spectroscopy, X-ray photoelectron spectroscopy and fluorescence spectrophotometer as well as other means of characterization. The surface morphology of the LBL film was analyzed by scanning electron microscope and atomic force microscopy.The study found that ZnTMPyP-PVP/PSS assembled multilayers show good3D configuration and could be used as heterogeneous catalysts in catalytic oxidation of azo dye reaction.