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Assessing the Influence of Zeolite Composition on Oxygen-Bridged Diamino Dicopper(II) Complexes in Cu-CHA DeNO_x Catalysts by Machine Learning-Assisted X-ray Absorption Spectroscopy.

ABSTRACT: Cu-exchanged chabazite is the catalyst of choice for NO_x abatement in diesel vehicles aftertreatment systems via ammonia-assisted selective catalytic reduction (NH₃-SCR). Herein, we exploit in situ X-ray absorption spectroscopy powered by wavelet transform analysis and machine learning-assisted fitting to assess the impact of the zeolite composition on NH₃-mobilized Cu-complexes formed during the reduction and oxidation half-cycles in NH₃-SCR at 200 °C. Comparatively analyzing well-characterized Cu-CHA catalysts, we show that the Si/Al ratio of the zeolite host affects the structure of mobile dicopper(II) complexes formed during the oxidation of the [Cu^I(NH₃)₂]⁺ complexes by O₂. Al-rich zeolites promote a planar coordination motif with longer Cu-Cu interatomic distances, while at higher Si/Al values, a bent motif with shorter internuclear separations is also observed. This is paralleled by a more efficient oxidation at a given volumetric Cu density at lower Si/Al, beneficial for the NO_x conversion under NH₃-SCR conditions at 200 °C.

SUBMITTER: Martini A

PROVIDER: S-EPMC9272442 | biostudies-literature |

REPOSITORIES: biostudies-literature

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SO2 Poisoning of Cu-CHA deNO x Catalyst: The Most Vulnerable Cu Species Identified by X-ray Absorption Spectroscopy.

Project description:Cu-exchanged chabazite zeolites (Cu-CHA) are effective catalysts for the NH3-assisted selective catalytic reduction of NO (NH3-SCR) for the abatement of NO x emission from diesel vehicles. However, the presence of a small amount of SO2 in diesel exhaust gases leads to a severe reduction in the low-temperature activity of these catalysts. To shed light on the nature of such deactivation, we characterized a Cu-CHA catalyst under well-defined exposures to SO2 using in situ X-ray absorption spectroscopy. By varying the pretreatment procedure prior to the SO2 exposure, we have selectively prepared CuI and CuII species with different ligations, which are relevant for the NH3-SCR reaction. The highest reactivity toward SO2 was observed for CuII species coordinated to both NH3 and extraframework oxygen, in particular for [CuII 2(NH3)4O2]2+ complexes. Cu species without either ammonia or extraframework oxygen ligands were much less reactive, and the associated SO2 uptake was significantly lower. These results explain why SO2 mostly affects the low-temperature activity of Cu-CHA catalysts, since the dimeric complex [CuII 2(NH3)4O2]2+ is a crucial intermediate in the low-temperature NH3-SCR catalytic cycle.

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