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.

Cu-exchanged chabazite is the catalyst of choice for NO x abatement in diesel vehicles aftertreatment systems via ammonia-assisted selective catalytic reduction (NH 3 -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 NH 3 -mobilized Cu-complexes formed during the reduction and oxidation half-cycles in NH 3 -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 (NH 3 ) 2 ] + complexes by O 2 . 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 NH 3 -SCR conditions at 200 °C.