Matrix-assisted laser desorption/ionisation mass spectrometry in the study of polycondensation of Ti(OBun)4 in the presence of Si(OEt)4

The hydrolysis-polycondensation behaviour of alcoholic solutions containing Si(OEt)4 and Ti(OBun)4, in different molar ratios (Si/Ti = 10–0.2), was analysed by laser desorption/ionisation (LDI) and matrix-assisted laser desorption/ionisation (MALDI) mass spectrometry. The solutions were prepared using operating conditions usually employed in the sol-gel synthesis of SiO2-TiO2 materials. In accord with the well-known procedures for controlling the different chemical reactivities of the alkoxides, the pre-hydrolysis of the slower reacting silicon ethoxide and the chelation by acetylacetone of the faster reacting titanium butoxide were performed before mass spectrometric analysis. While LDI-MS did not provide evidence for the presence of mixed Si-Ti species in samples obtained from these reactions, MALDI-MS of samples diluted with chloroform and using 2,5-dihydroxybenzoic acid (DHB) as matrix led to detection of various oligomers with different contents of Si and Ti atoms. The results suggest that the formation of Si-Ti mixed oligomers seems to be the favoured process, especially for solutions in which one of the two components is diluted. Copyright © 2003 John Wiley & Sons, Ltd.