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Part I: A Comparative Thermal Aging Study on the Regenerability of Rh/Al2O3 and Rh/CexOy-ZrO2 as Model Catalysts for Automotive Three Way Catalysts
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Catalysts 2015, 5(4), 1797-1814; doi:10.3390/catal5041797

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

1
Earth and Environmental Engineering Department, Columbia University, 500 West 120th Street, New York, NY 10027, USA
2
BASF Corporation, Research and Development Center, 25 Middlesex Essex Tpke, Iselin, NJ 08830-0770, USA
*
Author to whom correspondence should be addressed.
Academic Editor: Jae-Soon Choi
Received: 30 August 2015 / Revised: 8 October 2015 / Accepted: 8 October 2015 / Published: 23 October 2015
(This article belongs to the Special Issue Automotive Emission Control Catalysts)
View Full-Text   |   Download PDF [887 KB, uploaded 23 October 2015]   |  

Abstract

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/CexOy-ZrO2 (CZO) as model catalysts. The effect on the Rh component was presented in our companion paper Part I. Moderate support sintering and Pd-CexOy 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. View Full-Text
Keywords: automotive three way catalysts (TWC); Pd/Al2O3; Pd/CexOy-ZrO2; fuel shutoff aging; catalyst deactivation; fuel rich regeneration; metal sintering; metal-support interaction automotive three way catalysts (TWC); Pd/Al2O3; Pd/CexOy-ZrO2; fuel shutoff aging; catalyst deactivation; fuel rich regeneration; metal sintering; metal-support interaction
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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MDPI and ACS Style

Zheng, Q.; Farrauto, R.; Deeba, M. Part II: Oxidative Thermal Aging of Pd/Al2O3 and Pd/CexOy-ZrO2 in Automotive Three Way Catalysts: The Effects of Fuel Shutoff and Attempted Fuel Rich Regeneration. Catalysts 2015, 5, 1797-1814.

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