Activation of Surface Oxygen Sites in a Cobalt-Based Perovskite Model Catalyst for CO Oxidation

Anionic redox chemistry is becoming increasingly important in explaining the intristic catalytic behavior in transition-metal oxides and improving catalytic activity. However, it is a great challenge to activate lattice oxygen in noble-metal-free perovskites for obtaining active peroxide species. Here, we take La_0.4Sr_0.6CoO_3-δ as a model catalyst and develop an anionic redox activity regulation method to activate lattice oxygen by tuning charge transfer between Co⁴⁺ and O^2-. Advanced XAS and XPS demonstrate that our method can effectively decrease electron density of surface oxygen sites (O^2-) to form more reactive oxygen species (O^{2- x}), which reduces the activation energy barriers of molecular O₂ and leads to a very high CO catalytic activity. The revealing of the activation mechanism for surface oxygen sites in perovskites in this work opens up a new avenue to design efficient solid catalysts. Furthermore, we also establish a correlation between anionic redox chemistry and CO catalytic activity.