4.8 Article

Palladium/Ferrierite versus Palladium/SSZ-13 Passive NOx Adsorbers: Adsorbate-Controlled Location of Atomically Dispersed Palladium(II) in Ferrierite Determines High Activity and Stability**

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出版社

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202107554

关键词

adsorption; NOx adsorbers; NOx uptake; release cycling; palladium; zeolites

资金

  1. U.S. Department of Energy, Energy Efficiency and Renewable Energy, Vehicle Technology Office
  2. Department of Energy's Office of Biological and Environmental Research at Pacific Northwest National Laboratory (PNNL)
  3. DOE by Battelle Memorial Institute [DE-AC06-76RL01830]
  4. CLEERS (Crosscut Lean Exhaust Emissions Reduction Simulations)
  5. U.S. Department of Energy (DOE) Vehicle Technologies Office

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Pd-loaded FER and SSZ-13 zeolites were compared as low-temperature passive NOx adsorbers under practical conditions, showing that the NO release temperature decreased with an increase in CO concentration for both adsorbers. The presence of CO activated Pd ions in FER, leading to improved NOx storage, while also explaining the high resistance of Pd/FER to hydrothermal aging.
Pd-loaded FER and SSZ-13 zeolites as low-temperature passive NOx adsorbers (PNA) are compared under practical 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 in PNA. The NO release temperature of both adsorbers decreases gradually with an increase in CO concentration from a few hundred to a few thousand ppm. This beneficial effect results from local nano-hot spot formation during CO oxidation. Dissimilar to Pd/SSZ-13, increasing the CO concentration above approximate to 1000 ppm improves the NOx storage significantly for Pd/FER, which was attributed to the presence of Pd ions in FER sites that are 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 800 degrees C 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 (hydro)thermally stable and active PNA materials.

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