On A-doping strategy for tuning the TWC catalytic performance of perovskite based catalysts

Several perovskites of the type La1-xAxCo0.5Cu0.5O3 (A = K, Sr, Ba; x = 0, 0.25, 0.5) and a Sr-doped understoichiometric one, have been prepared by citrate method aiming at application as noble metals free catalysts for automotive application. The catalysts have been characterized by BET, X-ray diffraction (XRD), Temperature Programmed Reduction (TPR), X-Ray Photoelectron Spectroscopy (XPS), and Scanning Electron Microscopy (SEM) and the effect of A-doping has been investigated. The catalytic activity was studied in model reactions (CO oxidation, CO assisted NO reduction), and in a complex three way catalysts (TWC) mixture approaching automotive exhaust composition at both stoichiometric and O2-limiting conditions and the obtained results are discussed in relation with characterization results. A-doping induces the formation of highly dispersed cubic CuO particles, as observed in the understoichiometric samples. Doping also influences the surface segregation. La segregation is observed in the undoped LaCo0.5Cu0.5O3 sample whereas K is surface segregated in La0.75K0.25Co0.5Cu0.5O3; Co segregates in the Ba-doped perovskite and Sr in the understoichiometric La0.35Sr0.35Co0.5Cu0.5O3. The reducibility (TPR) is altered by A-doping. The reactivity results suggest that in simple CO + O2 and CO + NO mixtures the activation temperature is increased by any doping, but at 400 °C the conversion in the CO assisted NO reduction is not significantly different with respect to the one obtained in the undoped catalyst. Activity with a more complex mixture, simulating actual engine exhaust, reveals the interesting activity of the Sr-doped catalysts, that outperform LaCo0.5Cu0.5O3 at both stoichiometric and O2-lean conditions. NO reduction can be achieved at lean O2 conditions, where it is quantitative from 400 °C. The possibility to reach similar or better activity by replacing the use of La, which is a Rare Earth Element, by using Sr is particularly interesting. Stability at high temperatures and at fast fluctuations of O2 in inlet stream for 50% Sr-doped catalyst confirms these results.