Nb effect in the nickel oxide-catalyzed low-temperature oxidative dehydrogenation of ethane

Abstract

A method for the preparation of NiO and Nb–NiO nanocomposites is developed, based on the slow oxidation of a nickel-rich Nb–Ni gel obtained in citric acid. The resulting materials have higher surface areas than those obtained by the classical evaporation method from nickel nitrate and ammonium niobium oxalate. These consist in NiO nanocrystallites (7–13nm) associated, at Nb contents >3at.%., with an amorphous thin layer (1–2nm) of a niobium-rich mixed oxide with a structure similar to that of NiNb2O6. Unlike bulk nickel oxides, the activity of these nanooxides for low-temperature ethane oxidative dehydrogenation (ODH) has been related to their redox properties. In addition to limiting the size of NiO crystallites, the presence of the Nb-rich phase also inhibits NiO reducibility. At Nb content >5at.%, Nb–NiO composites are thus less active for ethane ODH but more selective, indicating that the Nb-rich phase probably covers part of the unselective, non-stoichiometric, active oxygen species of NiO. This geometric effect is supported by high-resolution transmission electron microscopy observations. The close interaction between NiO and the thin Nb-rich mixed oxide layer, combined with possible restructuration of the nanocomposite under ODH conditions, leads to significant catalyst deactivation at high Nb loadings. Hence, the most efficient ODH catalysts obtained by this method are those containing 3–4at.% Nb, which combine high activity, selectivity, and stability. The impact of the preparation method on the structural and catalytic properties of Nb–NiO nanocomposites suggests that further improvement in NiO-catalyzed ethane ODH can be expected upon optimization of the catalyst.