On the Redox Mechanism of Low-Temperature NH3 -SCR over Cu-CHA: A Combined Experimental and Theoretical Study of the Reduction Half Cycle

Abstract

Cu-CHA is the state-of-the-art catalyst for the Selective Catalytic Reduction (SCR) of NOx in vehicle applications. Although extensively studied, diverse mechanistic proposals still stand in terms of the nature of active Cu-ions and reaction pathways in SCR working conditions. Herein we address the redox mechanism underlying Low-Temperature (LT) SCR on Cu-CHA by an integration of chemical-trapping techniques, transient-response methods, operando UV/Vis-NIR spectroscopy with modelling tools based on transient kinetic analysis and density functional theory calculations. We show that the rates of the Reduction Half-Cycle (RHC) of LT-SCR display a quadratic dependence on Cu^II , thus questioning mechanisms based on isolated Cu^II -ions. We propose, instead, a Cu^II -pair mediated LT-RHC pathway, in which NO oxidative activation to mobile nitrite-precursor intermediates accounts for Cu^II reduction. These results highlight the role of dinuclear Cu complexes not only in the oxidation part of LT-SCR, but also in the RHC reaction cascade.

Keywords: Cu-CHA; NH3-SCR; nitrogen oxides; reaction mechanisms; reduction half-cycle.