The mobility of the copper cations acting as active sites for the selective catalytic reduction of nitrogen oxides with ammonia in Cu-CHA catalysts varies with temperature and feed composition. Herein, the migration of [Cu(NH₃)₂]⁺ complexes between two adjacent cavities of the chabazite structure, including other reactant molecules (NO, O₂, H₂O, and NH₃), in the initial and final cavities is investigated using ab initio molecular dynamics (AIMD) simulations combined with enhanced sampling techniques to describe hopping events from one cage to the other. We find that such diffusion is only significantly hindered by the presence of excess NH₃ or NO in the initial cavity, since both reactants form with [Cu(NH₃)₂]⁺ stable intermediates which are too bulky to cross the 8-ring windows connecting the cavities. The presence of O₂ modifies strongly the interaction of NO with Cu⁺. At low temperatures, we observe NO detachment from Cu⁺ and increased mobility of the [Cu(NH₃)₂]⁺ complex, while at high temperatures, NO reacts spontaneously with O₂ to form NO₂. The present simulations give evidence for recent experimental observations, namely, an NH₃ inhibition effect on the SCR reaction at low temperatures, and transport limitations of NO and NH₃ at high temperatures. Our first principle simulations mimicking operating conditions support the existence of two different reaction mechanisms operating at low and high temperatures, the former involving dimeric Cu(NH₃)₂-O₂-Cu(NH₃)₂ species and the latter occurring by direct NO oxidation to NO₂ in one single cavity.

Cu-exchanged zeolites rely on mobile solvated Cu⁺ cations for their catalytic activity, but the role of the framework composition in transport is not fully understood. Ab initio molecular dynamics simulations can provide quantitative atomistic insight but are too computationally expensive to explore large length and time scales or diverse compositions. We report a machine-learning interatomic potential that accurately reproduces ab initio results and effectively generalizes to allow multinanosecond simulations of large supercells and diverse chemical compositions. Biased and unbiased simulations of [Cu(NH₃)₂]⁺ mobility show that aluminum pairing in eight-membered rings accelerates local hopping and demonstrate that increased NH₃ concentration enhances long-range diffusion. The probability of finding two [Cu(NH₃)₂]⁺ complexes in the same cage, which is key for SCR-NOx reaction, increases with Cu content and Al content but does not correlate with the long-range mobility of Cu⁺. Supporting experimental evidence was obtained from reactivity tests of Cu-CHA catalysts with a controlled chemical composition.