Hydrolysis of titanium alkoxides: Modification of the molecular precursor by acetic acid

Monolithic TiO2 gels can be reproducibly obtained when the hydrolysis of titanium alkoxides is performed in the presence of acetic acid. This carboxilic acid does not act only as an acid catalyst, but also as a ligand and changes the alkoxide precursor at a molecular level therefore modifying the whole hydrolysis condensation process. Infra-red experiments show that bidentate acetates replace OR groups and are directly bounded to the titanium. Both, chelating and bridging acetates, are observed, leading to Ti(OR)x(Ac)y. oligomers. Hydrolysis of this new molecular precursor removes first (OR) groups and bridging acetates. Chelating acetates are still observed in the gel. They can only be removed upon heating above 200 °C.