Deactivation Mechanism of Pd/CeO2-ZrO2 Three-Way Catalysts Analyzed by Chassis-Dynamometer Tests and in Situ Diffuse Reflectance Spectroscopy

摘要

The thermal deactivation of engine-aged Pd/CeO2-ZrO2 three-way catalysts was studied by chassis-dynamometer driving test cycles with cold start and in situ diffuse reflectance spectroscopy (DRS). The extent of the catalyst deactivation after engine-aging at 800-1000 degrees C was correlated with the microstructural evolution, which was analyzed by X-ray diffraction, X-ray absorption spectroscopy, electron microscopy, and a chemisorption technique. This suggests that deactivation is caused by degradation of the catalytically active sites in the three-phase boundary (TPB) region, where Pd, CeO2-ZrO2, and the gas phase meet. The time-resolved in situ DRS revealed that the reoxidation of Pd metal under fluctuating air-to-fuel ratios was retarded relative to the reduction of Pd oxide. The retardation is attributable to the oxygen storage in CeO2-ZrO2. In the fresh catalyst with a high dispersion, most Pd was close to the TPB. Conversely, after engine-aging at elevated temperatures, the retardation effect was less pronounced with respect to Pd particle growth. Grown into large Pd particles, the Pd at sufficient distances from the TPB was no longer affected by the oxygen storage. Consequently, from the ratios of the initial rate constants of the Pd oxidation and reduction under fluctuating air-to-fuel ratio conditions, we can understand the quality and/or quantity of the TPB site in engine-aged catalysts. This measure provides a useful index of the extent of catalyst deactivation.