Kinetic Monte Carlo Analysis Reveals Non-mean-field Active Site Dynamics in Cu–Zeolite-Catalyzed NOx Reduction

Copper-exchanged chabazite (Cu-CHA) zeolites are the preferred catalysts for the selective catalytic reduction of NOx with NH3. The low temperature (473 K) SCR mechanism proceeds through a redox cycle between mobile and ammonia-solvated Cu(I) and Cu(II) complexes, as demonstrated by multiple experimental and computational investigations. The oxidation step requires two Cu(I) to migrate into the same cha cage to activate O2 and form a binuclear Cu(II)-di-oxo complex. Prior steady state and transient kinetic experiments find that the apparent rate constants for oxidation (per Cu ion) are sensitive to catalyst composition and follow nonmean-field kinetics. We develop a nonmean-field kinetic model for NOx SCR that incorporates a composition-dependent Cu(I) volumetric footprint centered at anionic [AlO4]− tetrahedral sites on the CHA lattice. We use Bayesian optimization to parameterize a kinetic Monte Carlo model against available experimental composition-dependent SCR rates and in situ Cu(II) fractions. We find that both rates and Cu(II) fractions of a majority of catalyst compositions can be captured by single oxidation and reduction rate constants combined with a composition-dependent Cu(I) cation footprint, highlighting the contributions of both Cu and Al densities to steady-state SCR performance of Cu-CHA. The work illustrates a pathway for extracting robust molecular insights from the kinetics of a dynamic catalytic system.