Active Ni and Fe species on catalysts Ni/Al2O3 and NiFe/Al2O3 for the oxidative dehydrogenation (ODH) of ethane to ethylene assisted by CO2

•The iron addition decreased the crystal size of the NiO.•Spinel-type structures such as NiAl2O4, NiFe2O4, and FeAl2O4 are active species in the ODH of ethane.•The tetrahedral symmetry species are more selective for ethylene than octahedral symmetry.•The catalysts with similar NiO crystallite size displayed different metal-support interactions.•A strong metal-support interaction increases the selectivity and yield toward ethylene. Ni/Al2O3 and NiFe/Al2O3 catalysts were synthesized by incipient wetness impregnation and tested for oxidative dehydrogenation (ODH) of ethane to ethylene. The effect of Ni loading and Fe as a promoter for bimetallic catalysts were characterized by X-ray diffraction (XRD), Raman spectroscopy, ultraviolet-visible diffuse reflectance spectroscopy (UV-vis DRS), scanning electron microscopy (SEM), and temperature-programmed reduction (H2-TPR). The catalyst with 10 wt% Ni and 6.6 wt% Fe (NiFe32) displayed the highest ODH activity. XRD results showed smaller crystalline NiO (˂ 7 nm) for bimetallic catalysts than the monometallic ones. Raman results depicted NiOx species in the monometallic catalysts. The bimetallic catalysts exhibited spinel-type structures as NiFe2O4 and FeAl2O4 related to more active species in ODH of ethane. DRS results revealed that the higher ODH activity for bimetallic catalysts is related to a predominance of Ni and Fe in tetrahedral symmetry (Td) than octahedral symmetry (Oh). These suggest that tetrahedral symmetry species were more effective than octahedral symmetry. TPR profiles showed that the iron addition increased the nickel species with strong interaction with the support. This rearrangement of Ni and Fe species in octahedral and tetrahedral sites of the NiO and alumina lattice could explain the shift reduction temperatures for Ni species and the formation of the spinel-type structure in the bimetallic catalysts. A relation between the metal-support interaction and the selectivity toward ethylene was found. A higher strong metal-support interaction favors a better catalytic activity. [Display omitted]