Part II: Oxidative Thermal Aging of Pd/Al₂O₃ and Pd/Ce_xO_y-ZrO₂ in Automotive Three Way Catalysts: The Effects of Fuel Shutoff and Attempted Fuel Rich Regeneration

摘要

The Pd component in the automotive three way catalyst (TWC) experiences deactivation during fuel shutoff, a process employed by automobile companies for enhancing fuel economy when the vehicle is coasting downhill. The process exposes the TWC to a severe oxidative aging environment with the flow of hot (800 °C–1050 °C) air. Simulated fuel shutoff aging at 1050 °C leads to Pd metal sintering, the main cause of irreversible deactivation of 3% Pd/Al₂O₃ and 3% Pd/Ce_xO_y-ZrO₂ (CZO) as model catalysts. The effect on the Rh component was presented in our companion paper Part I. Moderate support sintering and Pd-Ce_xO_y interactions were also experienced upon aging, but had a minimal effect on the catalyst activity losses. Cooling in air, following aging, was not able to reverse the metallic Pd sintering by re-dispersing to PdO. Unlike the aged Rh-TWCs (Part I), reduction via in situ steam reforming (SR) of exhaust HCs was not effective in reversing the deactivation of aged Pd/Al₂O₃, but did show a slight recovery of the Pd activity when CZO was the carrier. The Pd+/Pd0 and Ce3+/Ce4+ couples in Pd/CZO are reported to promote the catalytic SR by improving the redox efficiency during the regeneration, while no such promoting effect was observed for Pd/Al₂O₃. A suggestion is made for improving the catalyst performance.