Automotive Three-Way Catalysts (TWC) were introduced more than 40 years ago. Despite that, the development of a sustainable TWC still remains a critical research topic owing to the increasingly stringent emission regulations together with the price and scarcity of precious metals. Among other material classes, perovskite-type oxides are known to be valuable alternatives to conventionally used TWC compositions and have demonstrated to be suitable for a wide range of automotive applications, ranging from TWC to Diesel Oxidation Catalysts (DOC), from NO x Storage Reduction catalysts (NSR) to soot combustion catalysts. The interest in these catalysts has been revitalized in the past ten years by the introduction of the concept of catalyst regenerability of perovskite-based TWC, which is in principle well applicable to other catalytic processes as well, and by the possibility to reduce the amounts of critical elements, such as precious metals without seriously lowering the catalytic performance. The aim of this review is to show that perovskite-type oxides have the potential to fulfil the requirements (high activity, stability, and possibility to be included into structured catalysts) for implementation in TWC.

The ageing characteristics of flame-made 2 wt% Pd supported on YFeO 3 were analysed in comparison with a Pd/Al 2 O 3-CeO 2-ZrO 2 three-way catalyst (TWC) with respect to structural changes and catalytic performance for methane oxidation under stoichiometric reaction conditions. Thermal treatment under lean conditions (air, 900°C) resulted in slight decrease in the methane oxidation activity of the TWC. In marked contrast, YFeO 3-supported Pd catalysts exhibit an increase in activity after such treatment. Activity enhancement is even higher when the treatment was performed under stoichiometric conditions (air-fuel equivalence ratio, λ = 1, 900°C). To explain this observation, in-depth characterization (BET, STEM, OSCC, XAS, and CO chemisorption) of fresh and aged catalysts was performed. Both thermal and stoichiometric ageing cause a severe sintering of the support particles and the phase transformation from hexagonal to orthorhombic YFeO 3. Despite the absence of a mixed Pd-YFeO 3 phase, the growth of Pd particles appears to be limited under the λ = 1 atmosphere. In contrast to thermally aged catalysts where large PdO particles are formed, well-defined metallic Pd nanoparticles of 10-20 nm are present after stoichiometric ageing along with higher methane oxidation activity. Although it is tempting to conclude that metallic Pd is active for methane oxidation under the given conditions, reversible and periodic partial oxidation of the large metallic particles is observed in modulation excitation high energy X-ray diffraction (HXRD) experiments designed to simulate the oscillating redox conditions experienced during operation. These results indicate that large Pd particles exhibit improved methane oxidation activity but equally confirm that activity under stoichiometric conditions is the result of a delicate equilibrium dictated by the bulk-Pd/surface-PdO pair.

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