Operando QEXAFS Study of Pt–Fe Ammonia Slip Catalysts During Realistic Driving Cycles

Abstract

AbstractBifunctional Fe–Pt ammonia slip catalysts were studied by operando quick-scanning extended X-ray absorption fine structure spectroscopy (QEXAFS) under conditions mimicking rapid temperature variations that occur in an automotive exhaust gas aftertreatment system during real driving. Two catalysts, Pt/Al2O3 and Fe-ZSM-5, were tested individually, as mixtures and in dual bed arrangements. Applying QEXAFS allowed to track changes of active metal state with high time resolution. It uncovered a strong dependence of the active metal state on reaction conditions and catalyst bed layout. For example, proximity to platinum stabilized iron species in their more active oxidized state and led to higher Fe-ZSM-5 activity. On the contrary, isolated iron species were more susceptible to overreduction by ammonia which led to deactivation and low selectivity. The use of transient conditions uncovered the influence of non-equilibrium phenomena on catalytic performance under industrially relevant conditions. Specifically, the effect of ammonia storage on the increase of activity was shown. This was also accompanied by elevated N2O production not observed during tests with gradual heating. Additionally, unusually high NOx selectivity was detected for Fe-ZSM-5 under these conditions. Lastly, tracking catalyst state under dynamic reaction conditions disclosed that Fe-ZSM-5 activity did not grow directly with temperature increase but rather depended on the oxidation state of Fe and surface concentration of ammonia.