Decoding the Reactivity Enhancement of Ln₂Ce₂O₇ Compounds (Ln = Yb, Y, Tb, and Gd) for Soot Combustion: The Remarkable Contribution of Variable Valence A-Sites

The impact of variable valence A-sites on the redox property and reactivity of Ln(2)Ce(2)O(7) compounds in soot particulate combustion has been investigated. It was observed that Yb2Ce2O7, Y2Ce2O7, and Gd2Ce2O7 formed a rare earth C-type phase, while Tb2Ce2O7 formed a solid solution phase. Both Tb2Ce2O7 and Yb2Ce2O7 possess dual valence state A-sites, resulting in significantly more surface vacancies. Additionally, the advantageous solid solution phase structure of Tb2Ce2O7 leads to even more surface vacancies than Yb2Ce2O7, which is crucial to generate active oxygen sites. Moreover, the introduction of NO into the reaction feed enhances combustion activity by producing active surface monodentate nitrates. A catalyst with higher numbers of surface vacancies exhibits improved NO oxidation ability and better NO2 utilization efficiency. Consequently, the Tb2Ce2O7 compound demonstrates not only the best soot combustion activity, but also an optimal NOx-assistance effect. Therefore, it is concluded that variable valence A-site is the intrinsic factor to improve the reactivity of Ln(2)Ce(2)O(7) catalysts.