Nb-doped nickel oxides with Nb contents in the range from 1 to 20% and, for comparison, pure NiO, were characterized using in situ electrical conductivity measurements in correlation with their catalytic performances for the oxidative dehydrogenation (ODH) of ethane into ethylene. Their electrical conductivity was studied as a function of temperature and oxygen partial pressure and was followed with time during sequential exposures to air, ethane-air mixture (reaction mixture) and pure ethane in conditions similar to those of catalysis. All the oxides were p-type semiconductors under air. Their electrical conductivity in the reaction temperature range decreased in the following order: NiO > Nb(1)NiO > Nb(5)NiO > Nb(10)NiO > Nb(15)NiO > Nb(20)NiO. This correlates well with the catalytic activity expressed as the intrinsic rate of ethane consumption. All the catalysts were partially reduced under the reaction mixture in the reaction temperature range, an inverse correlation between their conductivity in these conditions and the ODH selectivity being observed. The ODH reaction of ethane takes place via a heterogeneous redox mechanism involving the surface lattice O(-) species.

Adding P to NiO leads to a decrease of ethane conversion with an increase in ODH selectivity.

Pure and M-doped nickel oxides with M = Li, Mg, Al, Ga, Ti, Nb, catalysts for the oxidative dehydrogenation of ethane into ethylene, were characterized by in situ electrical conductivity measurements. Their electrical conductivity was studied as a function of temperature and oxygen partial pressure and was followed with time during sequential exposures to air, an ethane-air mixture (reaction mixture) and pure ethane under conditions similar to those of catalysis. All the materials appeared to be p-type semiconductors under air with positive holes as the main charge carriers and their electrical conductivity decreased in the following order: Li-NiO > NiO > Mg-NiO > Nb-NiO > Ga-NiO > Al-NiO > Ti-NiO. All the catalysts remained p-type semiconductors in the reaction mixture at 400 °C. Correlations between the p-type semiconductivity and the catalytic properties have been evidenced. The reaction mechanism involves surface lattice O(-) species and can be assimilated to a Mars and van Krevelen mechanism.