  Perovskite structured transition metal oxides are important technological
materials for catalysis and solid oxide fuel cell applications. Their
functionality often depends on oxygen diffusivity and mobility through complex
oxide heterostructures, which can be significantly impacted by structural and
chemical modifications, such as doping. Further, when utilized within
electrochemical cells, interfacial reactions with other components (e.g. Ni-
and Cr-based alloy electrodes and interconnects) can influence the perovskite's
reactivity and ion transport, leading to complex dependencies that are
difficult to control in real-world environments. Here we use isotopic tracers
and atom probe tomography to directly visualize oxygen diffusion and transport
pathways across perovskite and metal-perovskite heterostructures, i.e. (Ni-Cr
coated) Sr-doped lanthanum ferrite (LSFO). Annealing in 18O2(g) results in
elemental and isotopic redistributions through oxygen exchange (OE) in the LSFO
while Ni-Cr undergoes oxidation via multiple mechanisms and transport pathways.
Complementary density functional theory (DFT) calculations at experimental
conditions provide rationale for OE reaction mechanisms and reveal a complex
interplay of different thermodynamic and kinetic drivers. Our results shed
light on the fundamental coupling of defects and oxygen transport in an
important class of catalytic materials.
