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

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.United States. Department of Energy. Solid State Energy Conversion Allianc (Core Technology Program Funding Opportunity Number DEFE0009435)Skoltech-MIT Center for Electrochemical EnergyOak Ridge National Laboratory. Scientific User Facilities DivisionUnited States. Department of Energy. Office of Basic Energy Science. Division of Materials Sciences and EngineeringNational Energy Research Scientific Computing Center (U.S.) (grant number CNMS2013-292