Inhibition Effect of Phosphorus Poisoning on the Dynamics and Redox of Cu Active Sites in a Cu-SSZ-13 NH3-SCR Catalyst for NOx Reduction

Phosphorus (P) stemming from biodiesel and/or lubricant oil additives is unavoidable in real diesel exhausts and deactivates gradually the Cu-SSZ-13 zeolite catalyst for ammonia-assisted selective catalytic NO_x reduction (NH₃-SCR). Here, the deactivation mechanism of Cu-SSZ-13 by P-poisoning was investigated by ex situ examination of the structural changes and by in situ probing the dynamics and redox of Cu active sites via a combination of impedance spectroscopy, diffuse reflection infrared Fourier transform spectroscopy, and ultraviolet-visible spectroscopy. We unveiled that strong interactions between Cu and P led to not only a loss of Cu active sites for catalytic turnovers but also a restricted dynamic motion of Cu species during low-temperature NH₃-SCR catalysis. Furthermore, the Cu^II ↔ Cu^I redox cycling of Cu sites, especially the Cu^I → Cu^II reoxidation half-cycle, was significantly inhibited, which can be attributed to the restricted Cu motion by P-poisoning disabling the formation of key dimeric Cu intermediates. As a result, the NH₃-SCR activity at low temperatures (200 °C and below) decreased slightly for the mildly poisoned Cu-SSZ-13 and considerably for the severely poisoned Cu-SSZ-13.