CeO2 nanocubes (c-CeO2), nanoparticles (p-CeO2), and nanorods calcined at 500 °C (r-CeO2-500) and 700 °C (r-CeO2-700) were used as supports to synthesize a series of Ni/CeO2 catalysts for the propane combustion and oxidative dehydrogenation of propane (ODHP) reactions. The Ni-CeO2 interaction greatly promotes the reducibility of CeO2, but CeO2 morphology-dependent Ni-CeO2 interaction was observed to form different speciation of Ni species (Ni2+ dissolved in CeO2, highly dispersive NiO, NiO aggregate) and oxygen species (strongly activated oxygen species, medially activated oxygen species, weakly activated oxygen species) in various Ni/CeO2 catalysts. Ni-CeO2 interaction is stronger in Ni/c-CeO2 catalysts than in other Ni/CeO2 catalysts. Different morphology-dependences of Ni/CeO2 catalysts in propane combustion and ODHP reactions were observed. The Ni/r-CeO2-500 catalyst with the largest strongly activated oxygen species is most catalytic active in the propane combustion reaction while the Ni/c-CeO2 catalyst with the largest amount of weakly activated oxygen species exhibits the best catalytic performance in the ODHP reaction. Thus, the CeO2 morphology engineering strategy is effective in finely tuning the metal-CeO2 interaction and the reactivity of oxygen species to meet the requirements of different types of catalytic oxidation reactions.
Keywords: CeO2 nanocrystals; Ni/c-CeO2 catalysts; morphology effect; oxidative dehydrogenation of propane; propane combustion; structure-activity relation.