Vanadia supported on TiO2SiO2 mixed oxide gels: Structure of the dispersed phase and activity for the selective catalytic reduction of NO with NH3
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Supported vanadia catalysts were prepared by reacting vanadyl triisopropoxide with titania-silica mixed oxide supports of fixed Ti: Si mol ratio (1 : 4 and 1 : 1), but of varying pore structure, surface area, and crystallinity. The latter properties were controlled by varying the sol-gel preparation parameters. Although the selectivity pattern for the selective catalytic reduction (SCR) remained essentially the same over all catalysts, the specific activity, defined on a per V5 basis, varied with the support. The vanadia content in all catalysts corresponded to less than one monolayer (defined as 0.10 wt%25 V2O5m2 or 11 μmol V5 /m2), and structural data indicate that the vanadia is well dispersed. Raman spectroscopy was used to differentiate between vanadia species immobilized on TiO2 and SiO2 domains, respectively. These results revealed that the mixed oxide gels can be categorized into two main types exhibiting titania- or silica-like behavior. A weak interaction that results from a two-stage hydrolysis procedure of the alkoxide precursors of the constituents is characteristic for silica-like supports. This contrasts with the titania-like behavior observed for TiO2SiO2 mixed oxides prepared by single-stage hydrolysis, where the vanadia-support interaction is strong. No crystalline V2O5 phases were detected. TPR profiles show that the reducibility of vanadia, as evidenced by shifts in the temperature of maximum hydrogen consumption, is dependent upon the composition and preparation method of the mixed gel supports. An increase in the value of Tmax can be correlated with a decrease in the turnover frequency (NO converted per V5 site) of the SCR reaction. © 1992.
Supported vanadia catalysts were prepared by reacting vanadyl triisopropoxide with titania-silica mixed oxide supports of fixed Ti: Si mol ratio (1 : 4 and 1 : 1), but of varying pore structure, surface area, and crystallinity. The latter properties were controlled by varying the sol-gel preparation parameters. Although the selectivity pattern for the selective catalytic reduction (SCR) remained essentially the same over all catalysts, the specific activity, defined on a per V5%2b basis, varied with the support. The vanadia content in all catalysts corresponded to less than one monolayer (defined as 0.10 wt%25 V2O5m2 or 11 μmol V5%2b /m2), and structural data indicate that the vanadia is well dispersed. Raman spectroscopy was used to differentiate between vanadia species immobilized on TiO2 and SiO2 domains, respectively. These results revealed that the mixed oxide gels can be categorized into two main types exhibiting titania- or silica-like behavior. A weak interaction that results from a two-stage hydrolysis procedure of the alkoxide precursors of the constituents is characteristic for silica-like supports. This contrasts with the titania-like behavior observed for TiO2SiO2 mixed oxides prepared by single-stage hydrolysis, where the vanadia-support interaction is strong. No crystalline V2O5 phases were detected. TPR profiles show that the reducibility of vanadia, as evidenced by shifts in the temperature of maximum hydrogen consumption, is dependent upon the composition and preparation method of the mixed gel supports. An increase in the value of Tmax can be correlated with a decrease in the turnover frequency (NO converted per V5%2b site) of the SCR reaction. © 1992.
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