Hydration effects on the molecular structure of silica-supported vanadium oxide catalysts: A combined IR, Raman, UV–vis and EXAFS study

The effect of hydration on the molecular structure of silica-supported vanadium oxide catalysts with loadings of 1–16 wt.% V has been systematically investigated by infrared, Raman, UV–vis and EXAFS spectroscopy. IR and Raman spectra recorded during hydration revealed the formation of V–OH groups, characterized by a band at 3660 cm−1. Hydroxylation was found to start instantaneously upon exposure to traces of water, reflecting a very high sensitivity of the supported vanadium oxide catalysts for H2O. Further hydration resulted in the appearance of a V–O–V vibration band located around 700 cm−1 pointing to the formation of di- or polymeric species. EXAFS analysis at 77 K indicated structural changes as the oxygen coordination changed from four to five. Moreover, a VV contribution was detected for the hydrated species. The IR, Raman and UV–vis data suggested a pyramidal anchoring of the dehydrated VOx species, whereas, the EXAFS data pointed to the presence of single V–O–Si bonded VOx species. This difference is attributed to water condensation effects at 77 K during EXAFS acquisition, resulting in a partial re-hydroxylation of the dehydrated samples, as confirmed by complementary IR and Raman analysis. Combining the results of this study with data from our previous studies [D.E. Keller, F.M.F. de Groot, D.C. Koningsberger, B.M. Weckhuysen, J. Phys. Chem. B 109 (2005) 10223; D.E. Keller, D.C. Koningsberger, B.M. Weckhuysen, J. Phys. Chem. B 110 (2006) 14313] as well as literature led to a reaction scheme in which a monomeric VOx species anchored by three Si–O–V bonds to the silica support (pyramidal-type structure) is transformed into a monomeric VOx species anchored by one Si–O–V bond (umbrella-type structure) by partial hydration of the catalyst material. This results in the formation of both V–O–H and Si–O–H bonds. At higher water pressures, larger vanadium oxide clusters are formed due to full hydration of the catalyst surface and a de-attachment of the vanadium oxide from the support surface. The results of this study provide evidence, that an umbrella-type structure (i.e., Si–O–VO(OH)2) could be present under catalytic conditions where H2O is a reaction product (e.g., partial oxidation of methanol to formaldehyde and oxidative dehydrogenation of alkanes). In other words, both the pyramidal ((Si–O)3–VO) and the umbrella (Si–O–VO(OH)2) model can exist at a support surface, their relative ratio depending on the hydration degree of the catalyst material. This study also illustrates that a corroborative characterization requires the use of multiple spectroscopic techniques applied at the same samples under almost identical measuring conditions