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.