A first-principles study of CO dissociative adsorption on iron nanoparticles supported on doped graphene

• Charge transfer from Fe nanoparticle to graphene affected by doping.
• Hybridization between Fe13 and graphene proportional to binding energy.
• Strong correlation between Fe13 binding energy and Fe d-electrons.
• CO dissociative binding energy is gauged by d-band center.

We study Fe13 nanoparticles supported on doped graphene and investigate the dissociative adsorption of CO on the nanoparticles using first-principle calculations. It is found that boron doping enhances the binding energy of Fe13 on the graphene but nitrogen doping reduces it. We show that difference in the work-function and subsequently in the charge transfer causes such behavior in the binding energies. Calculated d-band width and d-band center are well correlated with the Fe binding energy, mostly because of the orbital hybridization effect. We also show that the dissociative adsorption of CO on the Fe-graphene substrate is strongly correlated with the d-band center, which is in turn modulated by the doping concentration.