Surface characterization studies of TiO2 supported manganese oxide catalysts for low temperature SCR of NO with NH3

Abstract

A series of TiO2 supported manganese oxide catalysts were prepared by wet-impregnation method for the low temperature selective catalytic reduction (SCR) of NO with ammonia as a reductant. A combination of various physico-chemical techniques such as N2 physisorption, O2 chemisorption, TPR, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman were used to characterize the chemical environment of these catalysts. O2 chemisorption and XRD results suggest that Mn exist in a well-dispersed state at below 16.7wt.% of Mn on TiO2 anatase (Hombikat), 7.5wt.% on TiO2 rutile (Kemira) and P-25 (80% anatase+20% rutile), and in microcrystalline phase above these loading levels on respective support materials. These results also reveal that Mn interacts very well with pure anatase phase compared to rutile. XPS results of Mn/TiO2 anatase (Hombikat) catalysts illustrated the presence of MnO2 as a major phase (peak at 642.0eV) along with Mn2O3 as the minor phase at lower loadings. The presence of Mn2O3 disappears at higher loadings. The characterization results indicated that the manganese oxide exists as an isolated species at very low loadings, highly dispersed state probably as two dimensional monolayer species at intermediate loadings, polymeric or microcrystalline form of manganese oxide at higher (above monolayer capacity) loadings was envisaged. The catalytic performance of various amounts of Mn loaded on different TiO2 supported catalysts for low temperature SCR reaction at catalyst bed temperature 175°C under power plant conditions using GHSV=50,000h−1 was studied. The catalyst with 16.7wt.% Mn/TiO2 anatase (Hombikat) was found to be highly active and selective catalyst for this reaction. The Raman studies acted as complimentary tool to XPS in order to characterize the manganese oxides (MnO, Mn2O3, Mn3O4, MnO2). Raman data show that there is a strong interaction between the Mn oxides and the support, which is responsible for the impressive catalytic performance in comparison with other systems we investigated.