Iron Loading Effects in Fe/SSZ-13 NH3-SCR Catalysts: Nature of the Fe Ions and Structure–Function Relationships

Abstract

Using a traditional aqueous solution ion exchange method under a protecting atmosphere of N2, a series of Fe/SSZ-13 catalysts with various Fe loadings were synthesized. UV–vis, EPR, and Mossbauer spectroscopic methods, coupled with temperature-programmed reduction and desorption techniques, were used to probe the nature of the Fe sites. The major Fe species are extraframework Fe(III) species: [Fe(OH)2]+ (monomeric) and [HO–Fe–O–Fe–OH]2+ (dimeric). Larger oligomers with unknown nuclearity, poorly crystallized Fe oxide particles, together with isolated Fe2+ ions, are minor Fe-containing moieties. Reaction rate and Fe loading correlations, and temperature and Fe loading effects on SCR selectivities, suggest that isolated Fe3+ ions are the active sites for low-temperature standard SCR, and dimeric sites provide the majority of reactivity at higher temperatures. For NO oxidation, dimeric sites are the active centers. NH3 oxidation, on the other hand, is catalyzed by sites with higher nuclearity.