New insights into the NH3-selective catalytic reduction of NO over Cu-ZSM-5 as revealed by operando spectroscopy

Abstract

To control diesel vehicle NO_x emissions, Cu-exchanged zeolites have been applied in the selective catalytic reduction (SCR) of NO using NH₃ as reductant. However, the harsh hydrothermal environment of tailpipe conditions causes irreversible catalyst deactivation. The aggregation of isolated Cu²⁺ brings about unselective ammonia oxidation along with the main NH₃-SCR reaction. An unusual ‘dip’ shaped NO conversion curve was observed in the steamed zeolite Cu-ZSM-5, resulting from the undesired NH₃ oxidation that produced NO. Here we gain further insights into the NH₃-SCR reaction and its deactivation by employing operando UV-vis diffuse reflectance spectroscopy (DRS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) on fresh and steamed zeolite Cu-ZSM-5. We found that tetragonally distorted octahedral Cu²⁺ with associated NH₃ preferentially forms during low temperature NH₃-SCR (<250 °C) in fresh Cu-ZSM-5. The high coordination number of Cu²⁺ ensures the availability for high coverage of nitrate intermediates. Whilst in the steamed Cu-ZSM-5, [Cu_x(OH)_2x−1]⁺ oligomers/clusters in pseudo-tetrahedral symmetry with coordinated NH₃ accumulated during the low-temperature NH₃-SCR reaction. These clusters presented a strong adsorption of surface NH₃ and nitrates/nitric acid at low temperatures and therefore limited the reaction between surface species in the steamed Cu-ZSM-5. Further release of NH₃ with increased reaction temperature favors NH₃ oxidation that causes the drop of NO conversion at ∼275 °C. Moreover, competitive adsorption of NH₃ and nitrates/nitric acid occurs on shared Lewis-acidic adsorption sites. Prompt removal of surface nitrates/nitric acid by NO avoids the surface blockage and tunes the selectivity by alternating nitrate–nitrite equilibrium. The formation of adsorbed NO₂ and HNO_x points to the necessity of an acid adsorbent in practical applications. The structural similarity under the NH₃-SCR reaction and unselective NH₃ oxidation confirmed the entanglement of these two reactions above 250 °C.