Elucidating the reaction mechanism of SO2 with Cu-CHA catalysts for NH3-SCR by X-ray absorption spectroscopy

The application of Cu-CHA catalysts for the selective catalytic reduction of NOx by ammonia (NH3-SCR) in exhaust systems of diesel vehicles requires the use of fuel with low sulfur content, because the Cu-CHA catalysts are poisoned by higher concentrations of SO2. Understanding the mechanism of the interaction between the Cu-CHA catalyst and SO2 is crucial for elucidating the SO2 poisoning and development of efficient catalysts for SCR reactions. Earlier we have shown that SO2 reacts with the [Cu-2(II)(NH3)(4)O-2](2+) complex that is formed in the pores of Cu-CHA upon activation of O-2 in the NH3-SCR cycle. In order to determine the products of this reaction, we use X-ray absorption spectroscopy (XAS) at the Cu K-edge and S K-edge, and X-ray emission spectroscopy (XES) for Cu-CHA catalysts with 0.8 wt% Cu and 3.2 wt% Cu loadings. We find that the mechanism for SO2 uptake is similar for catalysts with low and high Cu content. We show that the SO2 uptake proceeds via an oxidation of SO2 by the [Cu-2(II)(NH3)(4)O-2](2+) complex, resulting in the formation of different Cu-I species, which do not react with SO2, and a sulfated Cu-II complex that is accumulated in the pores of the zeolite. The increase of the SO2 uptake upon addition of oxygen to the SO2-containing feed, evidenced by X-ray adsorbate quantification (XAQ) and temperature-programmed desorption of SO2, is explained by the re-oxidation of the Cu-I species into the [Cu-2(II)(NH3)(4)O-2](2+) complexes, which makes them available for reaction with SO2.