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Pd FER PNA Final version.pdf (2.72 MB)

Pd/FER vs Pd/SSZ-13 Passive NOx Adsorbers: Adsorbate-controlled Location of Atomically Dispersed Pd(II) in FER Determines High Activity and Stability

preprint
submitted on 03.06.2020, 23:07 and posted on 04.06.2020, 12:18 by Konstantin Khivantsev, Xinyi Wei, Libor Kovarik, Nicholas R. Jaegers, Eric D. Walter, Pascaline Tran, Yong Wang, János Szanyi

Pd-loaded FER and SSZ-13 zeolites as low-temperature passive NOx adsorbers (PNA) are compared under practically relevant conditions. Vehicle cold-start exposes the material to CO under a range of concentrations, necessitating a systematic exploration of the effect of CO on the performance of isolated Pd ions for PNA. NO release temperature of both adsorbers decreases gradually with the increase of CO concentration from a few hundred to a few thousand ppm. This beneficial effect results from local nano-“hot spots” formation during CO oxidation. Dissimilar to Pd/SSZ-13, increasing the CO concentration above ~1,000 ppm improves the NOx storage significantly for Pd/FER, attributed to the presence of a Pd ions in FER γ-site that is shielded from NOx. CO mobilizes this Pd atom to the NOx accessible position where it becomes active for PNA. This behavior explains the very high resistance of Pd/FER to hydrothermal aging: Pd/FER materials survive hydrothermal aging at 800⁰C in 10% H2O vapor for 16 hours with no deterioration in NOx uptake/release behavior. Thus, by allocating Pd ions to the specific microporous pockets in FER, we have produced very hydrothermally stable and active PNA materials with immediate practical applications.

Funding

The research at PNNL was supported by the U.S. Department of Energy, Energy Efficiency and Renewable Energy, Vehicle Technology Office. Experiments were conducted in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research at Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for the DOE by Battelle Memorial Institute under Contract DE-AC06-76RL01830. We acknowledge the support of CLEERS (Crosscut Lean Exhaust Emissions Reduction Simulations). CLEERS is an initiative funded by the U.S. Department of Energy (DOE) Vehicle Technologies Office to support the development of accurate tools for use in the design, calibration, and control of next generation engine/emissions control systems that maximize efficiency while complying with emissions regulations.

History

Email Address of Submitting Author

Konstantin.Khivantsev@pnnl.gov

Institution

Pacific Northwest National Laboratory

Country

United States

ORCID For Submitting Author

0000-0002-4810-586X

Declaration of Conflict of Interest

No conflicts to declare

Version Notes

Version 1.0

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