Revealing the Formation and Reactivity of Cage-Confined Cu Pairs in Catalytic NOx Reduction over Cu-SSZ-13 Zeolites by In Situ UV–Vis Spectroscopy and Time-Dependent DFT Calculation

The low-temperature mechanism of chabazite-type small-pore Cu-SSZ-13 zeolite, a state-of-the-art catalyst for ammonia-assisted selective reduction (NH3-SCR) of toxic NOx pollutants from heavy-duty vehicles, remains a debate and needs to be clarified for further improvement of NH3-SCR performance. In this study, we established experimental protocols to follow the dynamic redox cycling (i.e., CuII ↔ CuI) of Cu sites in Cu-SSZ-13 during low-temperature NH3-SCR catalysis by in situ ultraviolet-visible spectroscopy and in situ infrared spectroscopy. Further integrating the in situ spectroscopic observations with time-dependent density functional theory calculations allows us to identify two cage-confined transient states, namely, the O2-bridged Cu dimers (i.e., μ-η2:η2-peroxodiamino dicopper) and the proximately paired, chemically nonbonded CuI(NH3)2 sites, and to confirm the CuI(NH3)2 pair as a precursor to the O2-bridged Cu dimer. Comparative transient experiments reveal a particularly high reactivity of the CuI(NH3)2 pairs for NO-to-N2 reduction at low temperatures. Our study demonstrates direct experimental evidence for the transient formation and high reactivity of proximately paired CuI sites under zeolite confinement and provides new insights into the monomeric-to-dimeric Cu transformation for completing the Cu redox cycle in low-temperature NH3-SCR catalysis over Cu-SSZ-13.