Surface modification of nanocrystalline TiO2 particles (45 Å) with bidentate benzene derivatives (catechol, pyrogallol, and gallic acid) was found to alter optical properties of nanoparticles. The formation of the inner-sphere charge–transfer complexes results in a red shift of the semiconductor absorption compared to unmodified nanocrystallites. The binding structures were investigated by using FTIR spectroscopy. The investigated ligands have the optimal geometry for chelating surface Ti atoms, resulting in ring coordination complexes (catecholate type of binuclear bidentate binding–bridging) thus restoring in six-coordinated octahedral geometry of surface Ti atoms. From the Benesi–Hildebrand plot, the stability constants at pH 2 of the order 103 M−1 have been determined.
Unsaturated polyester resin (UPe)-based nanocomposites and fumed silica Aerosil R812S, R805 and R816, and R200 modified with phenyl terminal group, R200NPh, were prepared. UPe resins were synthesized from maleic anhydride and products of glycolysis, obtained by polyethylene terephthalate depolymerization with dipropylene glycol in the presence of tetrabutyl titanate catalyst. The obtained unsaturated polyesters were characterized by acid, hydroxyl, and iodine values and by FTIR and NMR analysis. The microstructural analysis of the prepared nanocomposites, performed by using transmission electron microscopy, confirmed that silica nanoparticles formed chain-like aggregates in the polymer matrix. The presence of modified silica nanoparticles had no influence on the glass transition temperature and thermal stability of polyester matrix.
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