Molecular structure of a supported VO4 cluster and its interfacial geometry as a function of the SiO2, Nb2O5, and ZrO2 support.
The influence of the support oxide on the molecular structure of a VO(4) cluster and its interfacial geometry has been determined for SiO(2), Nb(2)O(5), and ZrO(2) as supports. Raman, IR, UV-vis-NIR diffuse reflectance, electron spin resonance, and extended X-ray absorption fine structure (EXAFS) spectroscopies were used to characterize the supported vanadium oxide clusters after dehydration. It has been found that for all supports under investigation the vanadium ion is tetrahedral coordinated and consists of one V=O and three V-O bonds. For a VO(4)/SiO(2) catalyst it has been established that only one O neighbor is shared with the SiO(2) support via a V-O(b)-Si(support) bond with an angle of approximately 101 degrees (+/-0.5 degrees ) and a V...Si distance of 2.61 A. The absence of a second vanadium atom in the vicinity of the vanadium oxide cluster further subverts the classical assignment of the 920 cm(-1) Raman band to a V-O-V related vibration. The EXAFS results combined with structural modeling using Cerius(2) software lead to structural constraints, which imply a similar V-O(b)-M(support) interaction for Nb(2)O(5) and ZrO(2) as well. The V-O(b) and the V...M(support) distances depend on the geometry of each support surface. The results show that the classical model with three V-O(b)-M(support) bonds could not be experimentally observed with EXAFS under the applied measuring conditions. Additional experiments with IR and Raman spectroscopy under experimental conditions mimicking those of the EXAFS measurements reveal the presence of V-OH groups, giving further support for the presence of a O=V(OH)(2)-O(b)-M moiety at the support surface.
Keller
Daphne E
DE
Inorganic Chemistry and Catalysis, Department of Chemistry, Utrecht University, P.O. Box 80083, 3508 TB Utrecht, The Netherlands.
Koningsberger
Diek C
DC
Weckhuysen
Bert M
BM