Engineering topics

Wei, Xinyi

Publications and source records attributed to Wei, Xinyi.

5 records

DOE OSTI2022

Effect of framework Al pairing on NO storage properties of Pd-CHA passive NOx adsorbers

For this study, three Pd/H-CHA samples were prepared containing 53.0%, 10.8% and 6.5% paired Al sites at near fixed Si/Al ratio and similar Pd loading. According to H 2 temperature-programmed reduction, Pd was present almost exclusively as isolated cations in the two samples containing the higher concentrations of paired Al sites, whereas in the other sample PdO was also present. Simulated lean cold start tests on the fresh samples conducted in a microflow reactor showed that the sample containing PdO stored the lowest amount of NOx. When tested with CO/H 2 , the sample containing 53.0% paired Al sites showed significantly better storage capacity than the other samples and deactivated less rapidly upon sequential tests. Experiments using lean gasoline engine exhaust revealed similar trends. This study showed that a high concentration of paired Al sites in Pd/H-CHA is beneficial for NOx storage capacity, thermal durability, and minimizing deactivation in the presence of CO/H 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

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

Abstract 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 ≈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 °C in 10 % H 2 O 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.

Khivantsev, Konstantin↗

DOE OSTI2021

Development of Passive HC/NOx Trap Catalysts for Low Temperature Gasoline Applications

This project aimed to develop fundamental understanding of the chemistry of NO adsorption and reaction in Pd/zeolites so as to facilitate the rational design of passive NOx adsorber catalysts. The approach adopted combined both experimental and computational methods, which together allow a deeper understanding of the governing chemistry than the use of either method alone. The workflow began with Pd/H-CHA and Pd/H-BEA catalyst synthesis and characterization, in which the Si/Al ratio and Al siting were systematically varied. This was followed by catalyst evaluation using temperature-programed adsorption/desorption methods, as well as in situ spectroscopic measurements to probe the chemistry of NO adsorption. In parallel, the adsorption of NO and other relevant species (H 2 O, CO, HCs) was studied by means of quantum chemical calculations in order to rationalize the experimental data and provide additional insights. Catalyst aging studies were also performed with the aim of elucidating the mechanism of catalyst degradation. Finally, the insights gained in this project were applied to the preparation of an optimized HC/NOx adsorber catalyst, the performance of which was studied using exhaust gas from an engine dynamometer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

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

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 ˜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°C in 10% H 2 O vapor for 16 hours with no deterioration in NOx uptake/release behavior. Therefore, by allocating Pd ions to the specific microporous pockets in FER, we have produced (hydro)thermally stable and active PNA materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Structural Interconversion between Agglomerated Palladium Domains and Mononuclear Pd(II) Cations in Chabazite Zeolites

Palladium-exchanged zeolites are candidate materials for passive NO x adsorption in automotive exhaust aftertreatment, where mononuclear Pd cations behave as precursors to the purported NO x adsorption sites. Yet, the structures of zeolite lattice binding sites capable of stabilizing mononuclear Pd 2+ ions, and the mechanisms that interconvert agglomerated PdO and Pd domains into mononuclear Pd 2+ ions during Pd redispersion treatments, remain incompletely understood. In this work, we use a suite of spectroscopic methods and quantitative site titration techniques to characterize mononuclear and agglomerated Pd species on zeolites with varying material properties and treatment history. Aqueous-phase methods to introduce Pd onto NH 4 -form zeolites initially form mononuclear [Pd(NH 3 ) 4 ] 2+ complexes, but subsequent thermal treatments (573–723 K; air) lead to in situ formation of H 2 that first reduces Pd 2+ to metallic Pd domains, which are then oxidized by air to PdO domains. Progressive treatment of Pd-zeolites in air to higher temperatures (723–1023 K) converts larger fractions of agglomerated PdO to mononuclear Pd 2+ , as quantified by H 2 temperature programmed reduction, because higher temperature treatments facilitate Pd redispersion toward deeper locations within chabazite (CHA) crystallites, which is corroborated by complementary titrimetric and spectroscopic data. Pd-CHA zeolites synthesized with similar bulk Pd and framework Al content, but varying framework Al arrangement, provide evidence that six-membered rings (6-MR) hosting paired Al sites (Al–O–(Si–O) x –Al, x = 1, 2) stabilize Pd 2+ ions and that otherwise isolated Al sites can stabilize [PdOH] + species, identifiable by an IR OH stretch at 3660 cm –1 . These findings clarify the underlying chemical processes and gas environments that cause Pd agglomeration in zeolites and their subsequent redispersion to mononuclear Pd 2+ ions, which prefer binding at 6-MR paired Al sites in CHA, and indicate that higher temperature air treatments lead to more uniform Pd spatial distributions throughout zeolite crystallites.

36 MATERIALS SCIENCE↗