Strain‐Induced Orbital Contributions to Oxygen Electrocatalysis in Transition‐Metal Perovskites

Fernandez, Abel; Caretta, Lucas; Das, Sujit; Klewe, Christoph; Lou, Djamila; Parsonnet, Eric; Gao, Ran; Luo, Aileen; Shafer, Padraic; Martin, Lane W.

doi:10.1002/aenm.202102175

Title: Strain‐Induced Orbital Contributions to Oxygen Electrocatalysis in Transition‐Metal Perovskites

Journal Article · 24 October 2021 · Advanced Energy Materials

DOI: https://doi.org/10.1002/aenm.202102175 · OSTI ID:1834976

^[1];

^[1]; Klewe, Christoph ^[2]; Lou, Djamila ^[1];

^[1]; Gao, Ran ^[1]; Luo, Aileen ^[1];

^[2]; Martin, Lane W. ^[1]

Department of Materials Science and Engineering University of California Berkeley CA 94720 USA, Materials Sciences Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA
Advanced Light Source Lawrence Berkeley National Laboratory Berkeley CA 94720 USA

Abstract Epitaxial strain has been shown to produce dramatic changes to the orbital structure in transition metal perovskite oxides and, in turn, the rate of oxygen electrocatalysis therein. Here, epitaxial strain is used to investigate the relationship between surface electronic structure and oxygen electrocatalysis in prototypical fuel cell cathode systems. Combining high‐temperature electrical‐conductivity‐relaxation studies and synchrotron‐based X‐ray absorption spectroscopy studies of La _0.5 Sr _0.5 CoO ₃ and La _0.8 Sr _0.2 Co _0.2 Fe _0.8 O ₃ thin films under varying degrees of epitaxial strain reveals a strong correlation between orbital structure and catalysis rates. In both systems, films under biaxial tensile strain simultaneously exhibit the fastest reaction kinetics and lowest electron occupation in the d _z ² orbitals. These results are discussed in the context of broader chemical trends and electronic descriptors are proposed for oxygen electrocatalysis in transition metal perovskite oxides.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1834976

Journal Information:: Advanced Energy Materials, Journal Name: Advanced Energy Materials Journal Issue: 46 Vol. 11; ISSN 1614-6832

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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