Density functional theory study of N₂O decomposition catalyzed by Pd₄^-/0/+ clusters

Density functional theory (DFT) is used to investigate the N2O decomposition over Pd-4(-/0/+) clusters. The Eley-Rideal (ER) mechanism and the Langmuir-Hinshelwood (LH) mechanism are well established. The average binding energies show that the most stable structure of Pd-4(-/0/+) clusters is the tetrahedral configuration. For the Pd-4(-) cluster, the activation energies indicate that the rate-limiting step in two mechanisms is the formation of O-2, and the ER mechanism occurs more easily than the LH mechanism. While for the Pd-4(0) and Pd-4(+) clusters, the rate-limiting step in two mechanisms is the N2O decomposition to N-2, and the LH mechanism is more likely to process. Among all clusters, the Pd-4(-) cluster exhibits better catalytic activity compared with the Pd-4(0) and Pd-4(+) clusters.