Interfaces between dissimilar oxides are attracting significant interest for their potential role in accelerating charge transport and surface reaction kinetics. If well understood and controlled, they can provide a new way to enable high-performance solid-oxide fuel cells, separation membranes as well as fast switching memristors. For example, recent studies have demonstrated that cobaltite hetero-interfaces exhibit orders of magnitude faster oxygen reduction kinetics compared with either single phase. The interfacial strain fields, anisotropy, and electronic interactions between the two phases are the likely mediators behind such an unprecedented enhancement. The underlying mechanisms must be understood quantitatively, so that we can go beyond isolated and empirically found interface structures to rationally designing dissimilar oxide interfaces with superior properties. Towards this goal, we have investigated the local electronic structure and chemical state at nanometer resolution in model multilayer superlattices made of dissimilar cobaltites. To accomplish this, we used a novel combination of in-situ scanning tunneling spectroscopy and focused ion beam milling, complemented by x-ray photoelectron spectorsocpy depth profiling by high energy x-rays and by ion milling. We found that the wide band-gap cobaltite is electronically activated at elevated temperatures through an interfacial coupling with a reducible cobaltite. Combination of these experiments reveal that the reducible cobaltite provides electrons and oxygen vacancies into the wide band-gap cobaltite. Such electronic activation is expected to facilitate charge transfer to oxygen, and accelerate the reduction kinetics on the surface. There remains still a large amount of open questions on how dissimilar oxide interfaces impact oxygen diffusion and oxygen exchange on the surfaces. However, these recent results are encouraging for an improved understanding of oxide hetero-interfaces at elevated temperatures and could enable new interfaces with fast oxygen reduction kinetics.

Dissimilar oxide interfaces to accelerate oxygen reduction kinetics

248th National Meeting (2014)

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