Mixed conductivity, oxygen permeability and redox behavior of K2NiF4-type La2Ni0.9Fe0.1O4+δ

The total conductivity and Seebeck coefficient of La2Ni0.9Fe0.1O4+δ with K2NiF4-type structure, studied in the oxygen partial pressure range from 10−5 to 0.5 atm at 973–1223 K, were analyzed in combination with the steady-state oxygen permeability, oxygen non-stoichiometry and Mössbauer spectroscopy data in order to examine the electronic and ionic transport mechanisms. Doping of La2NiO4+δ with iron was found to promote hole localization on nickel cations due to the formation of stable Fe3+ states, although the electrical properties dominated by p-type electronic conduction under oxidizing conditions exhibit trends typical for both itinerant and localized behavior of the electronic sublattice. The segregation of metallic Ni on reduction, which occurs at oxygen chemical potentials close to the low-p(O2) stability boundary of undoped lanthanum nickelate, is responsible for the high catalytic activity towards partial oxidation of methane by the lattice oxygen of La2Ni0.9Fe0.1O4+δ as revealed by thermogravimetry and temperature-programmed reduction in dry CH4–He flow at 573–1173 K. A model for the oxygen permeation fluxes through dense La2Ni0.9Fe0.1O4+δ ceramics, limited by both bulk ionic conduction and surface exchange kinetics, was proposed and validated.