Understanding the active sites in
the catalyst is essential for
the design of efficient redox catalysis. A series of La(1–x)Ag
x
CoO3 (x = 0, 2.5, 5.0, and 7.5%) perovskite catalysts were synthesized
by sodium EDTA–citric acid complexation. La97.5Ag2.5CoO3 shows the best catalytic activity with the
solubility range at the perovskite A site, with T
90, T
50, and T
10 values of 448, 358, and 302 °C, respectively.
Moreover, with the presence of 5% steam, these values decreased to
404, 320, and 276 °C, respectively. H2-TPR and O2-TPD characterization confirmed that after the A site was
partially replaced by Ag+, the improvement of catalytic
performance was attributed to the easier formation of oxygen vacancies
and the enhancement of lattice oxygen transportation at low temperatures.
According to the in situ DRIFTS study, the La97.5Ag2.5CoO3 catalyst had two active centers, including
Co3+ and oxygen vacancies. Density functional theory calculations
verified that after adding Ag, the formation energy of surface oxygen
vacancies was decreased from 0.629 to 0.383 eV, and the oxygen vacancies
began to participate in the reaction as an active site. In addition,
the stable Co–O–N–Olatt adsorption
structure on LaAgCoO3 indicates that there was a synergistic
effect between the Co3+ and oxygen vacancy sites. From
the experimental and theoretical results, the cyclic redox mechanism
of NO-assisted soot oxidation over the LaAgCoO3 catalyst
is proposed. Our work reveals the activity evolution of oxygen vacancies
in perovskites and the interaction mechanism between the oxygen vacancies
and the adjacent metal sites, which provides a promising strategy
for the rational design of high-performance perovskite oxidation catalysts.