Computational Modeling Predicts the Stability of Both Pd⁺ and Pd²⁺ Ion-Exchanged into H-CHA

Passive NO_x adsorbers (PNA) using Pd/zeolites have emerged as a promising solution for the reduction of cold-start emissions from vehicle exhaust. However, the nature of the active sites and the mechanisms underlying NO_x adsorption in Pd/zeolites remain a subject of ongoing investigation. In this study, we employ quantum chemical simulations to investigate the structure of Pd species in cation-exchange sites at isolated Al and Al pairs in the 6-ring and 8-ring of the CHA framework, before the introduction of NO_x. Our calculations show that the speciation of Pd in these exchange sites strongly depends on the precise Al arrangement within the framework, as well as the operating conditions. Ionically dispersed Pd is found to be the most favorable species over a wide range of oxidizing and reducing conditions. Small oligomers of PdO and metallic Pd do not appear to be competitive at either isolated Al or Al pairs. Notably, our calculations show that ion exchange sites other than next-next-nearest neighbor Al pairs in the 6-ring will be preferentially occupied by Pd⁺ instead of Pd²⁺. The stability of Pd⁺ in the zeolite environment is an interesting contrast with its rareness in molecular Pd compounds. Nonetheless, a detailed analysis of the electronic structure shows that predicted Pd oxidation states are consistent with chemical intuition for all complexes investigated in this study. We also discuss the potential ambiguity in Pd characterization provided by typical experimental techniques such as XANES, EXAFS and UV-VIS, and highlight the need for additional EPR spectroscopy studies to further elucidate the initial Pd speciation in zeolites for PNA applications.