Dynamic catalysis of sub-nanometer metal clusters in oxygen dissociation

When the catalyst size decreases down to the nanometer or even sub-nanometer scale, their geometric and electronic structures are very different from the bulk materials. Especially, their structural dynamics can greatly affect catalytic performances. Herein, we report a theoretical study on oxygen dissociation on Ag 19 cluster, a critical step of ethylene epoxidation, to investigate the effect of structural dynamics on the catalytic activity. Combining ab initio molecular dynamics (AIMD) and free energy calculation, we obtain the free energy profiles under different temperatures and find sudden drops in the reaction free energy and barrier at certain temperature ranges. The reaction entropy change shows a positive peak because of the different melting temperatures between initial and final states. Additionally, we further investigate the oxygen diffusion process on the Ag cluster and compare it with the Au and Cu clusters. We find that weak adsorption of oxygen on the silver cluster leads to its facile diffusion and thus reduces the melting temperature of the cluster, therefore facilitating partial oxidation under mild conditions.