The chemical bonding of titanium in MFI-type zeolites (Ti-silicalite)
has been investigated using x-ray photoelectron spectroscopy (XPS). Di
fferent titanium silicalites as well as pure titania (anatase) have be
en analysed. We have found a distinctively higher binding energy of th
e Ti 2p photoelectrons in Ti-silicalite than in titania- or anatase-co
ntaining silicalite. Ti has the same oxidation state in all solids und
er study. We attribute the difference in binding energy to different o
xygen coordinations of the titanium in the framework of Ti-silicalite
(tetrahedral) and anatase (octahedral). This suggestion is supported b
y XPS-studies of TiO2-SiO2 glasses and TiO2-SiO2 mixed oxides where a
similar shift was found. Additional Raman-spectroscopic investigations
of the samples indicate the existence of tetrahedrally coordinated ti
tanium by the appearance of a characteristic band at approximately 965
cm-1. Non-framework TiO2 species containing octahedrally coordinated
titanium could also be distinguished by XPS. Further Ti incorporation
is indicated by the expansion of the unit cell which is related to the
Ti 2p intensity for the framework titanium.