Synergetic effect dependence on activated oxygen in the interface of NiOx-modified Pt nanoparticles for the CO oxidation from first-principles

Abstract

CO oxidation on NiO_x-modified Pt nanoparticles (NPs) was investigated by first-principles calculations and microkinetic methods. The binding energies of O₂ and CO on NiO_x/Pt suggest that CO adsorption is dominant and the CO oxidation mainly follows the Mars–van Krevelen (M–vK) mechanism. It was found that the interfacial O of NiO_x/Pt played a key role in the combination of adsorbed CO to O, as well as the O₂ dissociation. With a lower O vacancy formation energy, NiO_x/Pt_edge shows about four orders higher reaction rates than NiO_x/Pt₍₁₀₀₎. Microkinetic analysis suggests that the rate-determining step also depends on the active O at the interface. The calculations highlight the synergetic effect difference of NiO_x selectively deposited on the different sites of Pt NPs on the CO oxidation from the atomic reaction mechanism, and throws light on the high activity of CO oxidation on partially covered NiO_x/Pt_edge nanoparticles.