Lytvynenko A. Influence of structure of porous coordination polymers with bridging ligands of bipyridine type on processes of electrocatalytic activation of halogen-containing organic compounds

The thesis is devoted to determination of the influence of the structure and electrochemical properties of bridging ligands on the structure, sorption and electrochemical (in particular, electrocatalytic) properties of porous coordination polymers (PCPs) obtained on the basis of such ligands.The approaches to the preparation of electrochemically active electrode coatings on the basis of porous coordination polymers were developed in this work, and it was found that the potentials of reduction peaks of such coatings on cyclic voltammograms correlated with the potentials of reduction peaks of the corresponding bridging ligands in solutions. The possibility of electrocatalytic reduction of chloroform, CF3CHClBr and CF3CCl3 on such electrode coatings was shown. It was determined that the difference in electrocatalytic activity of a PCP in respect to different halogenalkanes - chloroform, freon R113 (CF2ClCFCl2) - changed in line with the sorption capacity of the PCP in respect to these halogenalkanes. It was shown that the currents of non-catalytic halogenalkane reduction could be increased by preliminary adsorption of this halogenalkane by PCP particles. It was determined that electrocatalytic activity of the investigated bridging ligands as molecular compounds in solutions increased with the increase of degree of delocalization of the electron on the highest occupied molecular orbital of the reduced form of the catalytically active species.