Influence of aluminium distribution on the diffusion mechanisms and pairing of [Cu(NH3)2]+ complexes in Cu-CHA

The performance of Cu-exchanged chabazite (Cu-CHA) for the ammonia-assisted selective catalytic reduction of NOx (NH3-SCR) depends critically on the presence of paired $${[{{{\rm{Cu}}}}{({{{{\rm{NH}}}}}_{3})}_{2}]}^{+}$$ [ Cu ( NH 3 ) 2 ] + complexes. Here, a machine-learning force field augmented with long-range Coulomb interactions is developed to investigate the effect of Al-distribution and Cu-loading on the mobility and pairing of $${[{{{\rm{Cu}}}}{({{{{\rm{NH}}}}}_{3})}_{2}]}^{+}$$ [ Cu ( NH 3 ) 2 ] + complexes. Performing unbiased and constrained molecular dynamics simulations, we obtain unique information inaccessible to first-principle calculations and experiments. The free energy barrier for $${[{{{\rm{Cu}}}}{({{{{\rm{NH}}}}}_{3})}_{2}]}^{+}$$ [ Cu ( NH 3 ) 2 ] + diffusion between CHA-cages depends sensitively on both the local and distant Al-distribution. Importantly, certain Al-distributions and arrangements of neighboring $${[{{{\rm{Cu}}}}{({{{{\rm{NH}}}}}_{3})}_{2}]}^{+}$$ [ Cu ( NH 3 ) 2 ] + and $${{{{{\rm{NH}}}}}_{4}}^{+}$$ NH 4 + cations make paired $${[{{{\rm{Cu}}}}{({{{{\rm{NH}}}}}_{3})}_{2}]}^{+}$$ [ Cu ( NH 3 ) 2 ] + complexes exothermic with respect to separated configurations. Our results suggest that the NH3-SCR activity can be enhanced by increasing the Cu-loading and Al-content. The dynamic interplay between $${[{{{\rm{Cu}}}}{({{{{\rm{NH}}}}}_{3})}_{2}]}^{+}$$ [ Cu ( NH 3 ) 2 ] + and $${{{{{\rm{NH}}}}}_{4}}^{+}$$ NH 4 + diffusion is crucial for the $${[{{{\rm{Cu}}}}{({{{{\rm{NH}}}}}_{3})}_{2}]}^{+}$$ [ Cu ( NH 3 ) 2 ] + mobility and stresses the need to explore large systems including long-range Coulomb interactions when studying diffusion of charged species in zeolites.