Enhanced carbon monoxide poisoning resistance of Pd/BEA by integrating with CeO2 for low temperature NO adsorption: The role of CeO2 on oxidizing carbon monoxide to CO32-

Passive NOx adsorption (PNA) represents a promising technology for controlling NOx emissions during cold starts. However, Pd/zeolite catalysts, the latest generation of PNA materials, suffer from serious deactivation under CO concentrations, owing to the CO induced aggregation of highly dispersed Pd sites to PdO particles. In this work, we found that the resistance to CO poisoning of Pd/BEA can be enhanced by integrating with CeO2 through physical mixing. The resulting CeO2 + Pd/BEA composite catalyst demonstrated a notably higher NOx storage capacity (with a NOx/Pd ratio of 1.3) compared to Pd/BEA (0.8). This improvement can be attributed to the interaction between CeO2 and the BEA support, which promoted the formation of nitrates on CeO2 during NO adsorption at 80 degrees C. More importantly, CeO2 effectively shielded Pd2+ ions from reduction by CO, with 88 % of Pd2+ ions remaining after CO exposure, significantly outperforming Pd/BEA, which retained only 66 %. Spectra characterization and DFT results indicate that the defects in CeO2 strongly trapped CO (- 0.973 eV), and the oxidation of trapped CO to CO32- by adsorbed oxygen (Oads) was exothermic (-1.35 eV), which reduced the exposure of Pd2+ ions to CO and inhibited the reduction and agglomeration of Pd2+ ions. While the composite sample still exhibited a slight reduction in NOx storage capacity after CO poisoning, with the NOx/Pd ratio decreasing from 1.3 to 0.9. The DFT simulation results indicate that the Ce-Oads bonds in CeO2 are weakened during the decomposition of the CO32- intermediate. This weakening could potentially facilitate the release of Oads, thereby reducing the Oads content as evidenced by spectral evidence. The decrease of Oads diminished nitrate formation on the CeO2 component in composite sample, resulting in the decline of NOx storage capacity after CO poisoning.