Ab initio density functional theory was used to investigate the adsorption of oxygen molecule on the nickel-rich pentlandite (110) surface, which is important for mineral extraction. The three most reactive adsorption sites: Fe-top, Ni-top, and fcc-hollow have been considered. Firstly, the non-adsorbed pentlandite surface reflects the Ni atoms relaxing inwards. Consequently, their electronic structure showed high Fe 3d-orbital contribution than the Ni 3d-orbitals at the EF (indicating that the Fe atoms are more reactive than Ni). Secondly, the O2-adsorbed surface predicted lowest adsorption energy for Fe-top (−1.902 eV), as a more spontaneous reaction is likely to occur than on fcc-hollow (−1.891 eV) and Ni-top (−0.040 eV) sites, suggesting Fe preferential oxidation. The density of states indicates that the O2 show prevalence of electrons in the πp* antibonding orbitals, and are reduced to zero states at the valence band on metal-bonded oxygen (O1). The σp* orbital is observed to reside just above the EF for Fe-top and fcc-hollow site, while on Ni-top is half-occupied for both metal-bonded oxygen (O1) and terminal oxygen (O2). Finally, the isosurface charge density difference showed electron (charge) depletion on Ni/Fe metals and accumulation on the O2 molecule. Bader analysis indicated that the oxidized Fe and Ni atoms adopt more positive charge, while O2 on Fe-top atoms possesses more negative charge than on Ni-top, resulting with O1 possessing a smaller charge than O2 atom.
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