Mechanisms of CH₄ activation over oxygen-preadsorbed transition metals by ReaxFF and AIMD simulations

The chemisorbed oxygen usually promotes the CH bond activation over less active metals like IB group metals but has no effect or even an inhibition effect over more active metals like Pd based on the static electronic structure study. However, the understanding in terms of dynamics knowledge is far from complete. In the present work, methane dissociation on the oxygen-preadsorbed transition metals including Au, Cu, Ni, Pt, and Pd is systemically studied by reactive force field (ReaxFF). The ReaxFF simulation results indicate that CH₄ molecules mainly undergo the direct dissociation on Ni, Pt, and Pd surfaces, while undergo the oxygen-assisted dissociation on Au and Cu surfaces. Additionally, the ab initio molecular dynamics (AIMD) simulations with the umbrella sampling are employed to study the free-energy changes of CH₄ dissociation, and the results further support the CH₄ dissociation pathway during the ReaxFF simulations. The present results based on ReaxFF and AIMD will provide a deeper dynamic understanding of the effects of pre-adsorbed oxygen species on the CH bond activation compared to that of static DFT.