By
depositing ceria on the surface of yttrium-stabilized zirconia
(YSZ) nanocrystals and further activation under high-temperature reducing
conditions, a 13% mol. CeO2/YSZ catalyst structured as
subnanometer thick, pyrochlore-type, ceria-zirconia islands has been
prepared. This nanostructured catalyst depicts not only high oxygen
storage capacity (OSC) values but, more importantly, an outstandingly
stable redox response upon oxidation and reduction treatments at very
high temperatures, above 1000 °C. This behavior largely improves
that observed on conventional ceria-zirconia solid solutions, not
only of the same composition but also of those with much higher molar
cerium contents. Advanced scanning transmission electron microscopy
(STEM-XEDS) studies have revealed as key not only to detect the actual
state of the lanthanide in this novel nanocatalyst but also to rationalize
its unusual resistance to redox deactivation at very high temperatures.
In particular, high-resolution X-ray dispersive energy studies have
revealed the presence of unique bilayer ceria islands on top of the
surface of YSZ nanocrystals, which remain at surface positions upon
oxidation and reduction treatments up to 1000 °C. Diffusion of
ceria into the bulk of these crystallites upon oxidation at 1100 °C
irreversibly deteriorates both the reducibility and OSC of this nanostructured
catalyst.