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The temporary storage of oxygen in a solid catalyst is imperative for many important industrial oxidation reactions in the gas phase, for instance the post-treatment of automotive exhaust gas. CeO2 is a promising catalyst for the HCl oxidation (Deacon process) in order to recover Cl2. Employing shape- controlled CeO2 nanoparticles (cubes, octahedrons, rods) with facets of preferential orientations ((100), (111), (110)), we studied the activity and stability under two reaction conditions (harsh: Ar:HCl:O2 = 6:2:2 and mild: Ar:HCl:O2 = 7:1:2). It turns out that both activity and stability are structure sensitive. In terms of space time yield (STY), the rods are the most active particles, followed by the cubes and finally the octahedrons. Ceria also possesses high OSC (oxygen storage capacity) which is a measure of the oxygen quantity that material can store and release. This makes ceria suitable for redox reactions which usually follow Mars-van Krevelen mechanism (surface oxygen atoms directly involved in reactions). A peculiar mixed Ce-Zr (1:1) oxide, the ordered κ-phase, is a promising catalytic material exhibiting an extraordinarily high oxygen storage capacity (OSC) and high thermal and chemical stability. We elucidate the temperature-dependent transformation between the pyrochlore pyr-Ce2Zr2O7.3 and κCe2Zr2O8 phase upon oxygen uptake by in-situ X-ray diffraction, X-ray absorption and in-situ Raman spectroscopy, providing insights into the electronic and structural changes on the atomic level, which are at the heart of the extraordinarily high OSC. We demonstrate that the Ce3+ concentration can be followed during transformation in-situ by Raman spectroscopy of the electronic spin flip in the f-shell of Ce3+. The catalytic activity of the κ-Ce2Zr2O8 phase has been investigated without an additional active component such as Pt: While the high OSC of the kappa phase is beneficial for the oxidation of CO, the oxidation of HCl turns out to be not affected by the high OSC.

Temporary storage of oxygen in a solid catalyst is imperative for many important industrial oxidation reactions in the gas phase, for instance the post-treatment of automotive exhaust gas. A peculiar mixed Ce–Zr (1:1) oxide, the ordered κ-Ce2Zr2O8 phase, is a promising catalytic material exhibiting an extraordinarily high oxygen storage capacity (OSC) and high thermal and chemical stability. We elucidate the temperature-dependent transformation between the pyrochlore pyr- Ce2Zr2O7 and κ-Ce2Zr2O8 phase upon oxygen uptake by in situ X-ray diffraction, X-ray absorption, and in situ Raman spectroscopy, providing insights into the electronic and structural changes on the atomic level, which are at the heart of the extraordinarily high OSC. We demonstrate that the Ce3+ concentration can be followed during transformation in situ by Raman spectroscopy of the electronic spin flip in the f-shell of Ce3+. The catalytic activity of the κ-Ce2Zr2O8 phase was investigated without an additional active component such as noble metals (Pt, etc.). While the high OSC of the κ-phase is beneficial for the oxidation of CO, the oxidation of HCl turns out to be unaffected by the high OSC.