Screening Ba0.9A0.1MnO3 and Ba0.9A0.1Mn0.7Cu0.3O3 (A = Mg, Ca, Sr, Ce, La) Sol-Gel Synthesised Perovskites as GPF Catalysts

Abstract

Ba_0.9A_0.1MnO₃ (BM-A) and Ba_0.9A_0.1Mn_0.7Cu_0.3O₃ (BMC-A) (A = Mg, Ca, Sr, Ce, La) perovskite-type mixed oxides were synthesised, characterised, and used for soot oxidation in simulated Gasoline Direct Injection (GDI) engine exhaust conditions. The samples have been obtained by the sol-gel method in an aqueous medium and deeply characterised. The characterization results indicate that the partial substitution of Ba by A metal in BaMnO₃ (BM) and BaMn_0.7Cu_0.3O₃ (BMC) perovskites: (i) favours the hexagonal structure of perovskite; (ii) improves the reducibility and the oxygen desorption during Temperature-Programmed Desorption (O₂-TPD) tests and, consequently, the oxygen mobility; (iii) mantains the amount of oxygen vacancies and of Mn(IV) and Mn(III) oxidation states, being Mn(IV) the main one; and (iv) for Ba_0.9A_0.1Mn_0.7Cu_0.3O₃ (BMC-A) series, copper is partially incorporated into the structure. The soot conversion data reveal that Ba_0.9La_0.1Mn_0.7Cu_0.3O₃ (BMC-La) is the most active catalyst in an inert (100% He) reaction atmosphere, as it presents the highest amount of copper on the surface, and that Ba_0.9Ce_0.1MnO₃ (BM-Ce) is the best one if a low amount of O₂ (1% O₂ in He) is present, as it combines the highest emission of oxygen with the good redox properties of Ce(IV)/Ce(III) and Mn(IV)/Mn(III) pairs.

Keywords: GDI engines; calcium; cerium; copper; lanthanum; magnesium; perovskite; soot oxidation; strontium.