Kinetics of Oxygen Surface Exchange on Epitaxial Ruddlesden–Popper Phases and Correlations to First-Principles Descriptors

Abstract

Through alignment of theoretical modeling with experimental measurements of oxygen surface exchange kinetics on (001)-oriented La[subscript 2–x]Sr[subscript x]MO[subscript 4+δ] (M = Co, Ni, Cu) thin films, we demonstrate here the capability of the theoretical bulk O 2p-band centers to correlate with oxygen surface-exchange kinetics of the Ruddlesden–Popper oxide (RP[subscript 214]) (001)-oriented thin films. In addition, we demonstrate that the bulk O 2p-band centers can also correlate with the experimental activation energies for bulk oxygen transport and oxygen surface exchange of both the RP[subscript 214] and the perovskite polycrystalline materials reported in the literature, indicating the effectiveness of the bulk O 2p-band centers in describing the associated energetics and kinetics. We propose that the opposite slopes of the bulk O 2p-band center correlations between the RP[subscript 214] and the perovskite materials are due to the intrinsic mechanistic differences of their oxygen surface exchange kinetics and bulk anionic transport.