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

CO oxidation on NiOx-modified Pt nanoparticles (NPs) was investigated by first-principles calculations and microkinetic methods. The binding energies of O-2 and CO on NiOx/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 NiOx/Pt played a key role in the combination of adsorbed CO to O, as well as the O-2 dissociation. With a lower O vacancy formation energy, NiOx/Pt-edge shows about four orders higher reaction rates than NiOx/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 NiOx 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 NiOx/Pt-edge nanoparticles.

Automated summary

The CO oxidation reaction on NiOx-modified Pt nanoparticles follows the Mars-van Krevelen mechanism, where the interfacial O on NiOx/Pt plays a key role in the combination of adsorbed CO to O. The NiOx/Pt-edge exhibits higher reaction rates due to a lower O vacancy formation energy.