Redox Dynamics of Pd Supported on CeO2-ZrO2 during Oxygen Storage/Release Cycles Analyzed by Time-Resolved in Situ Reflectance Spectroscopy

In situ time-resolved diffuse reflectance spectroscopy provided the redox dynamics of Pd nanoparticles supported on an oxygen storage material CeO2-ZrO2 (CZ) under lean/rich perturbation conditions. Because the reflectance at 450 nm is sensitive to the Pd oxidation state but is not affected by the redox of Ce3+/Ce4+ species of CZ, the real-time Pd redox can be monitored every second during oxygen storage/release in simulated engine combustion exhaust gas (CO-C3H6-NO-O-2) corresponding to gasoline air-to-fuel ratios of 14.1 (rich) and 15.0 (lean). Although a large amount of O-2 was stored by CZ upon the rich-to-lean switch, the rate of Pd oxidation during this event was found to be much more moderate compared to that with a reference catalyst, Pd/Al2O3. Because rapid oxygen uptake by CZ reduces the local O-2 partial pressure near the surface, the oxidation of Pd should be retarded. This can preserve active metallic Pd and thus contribute to longer retention of high NO reduction efficiency even under the lean condition. However, the reduction of Pd oxide (PdO) upon reverse (lean-to-rich) switching occurred at a similar rate irrespective of the support material. The metallic Pd deposits near the interface with CZ promote the catalytic activation of reducing gases (CO and C3H6), resulting in significant oxygen release from CZ. The temperature dependence of the redox rate demonstrates that oxidation of metallic Pd to PdO is much slower than reduction over Pd/CZ, whereas oxidation is faster than reduction over Pd/Al2O3. The preservation of active metallic Pd under lean/rich perturbation conditions is another key role of the oxygen storage CZ cocatalyst.