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Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal–air batteries

A Corrigendum to this article was published on 22 July 2011

This article has been updated


The prohibitive cost and scarcity of the noble-metal catalysts needed for catalysing the oxygen reduction reaction (ORR) in fuel cells and metal–air batteries limit the commercialization of these clean-energy technologies. Identifying a catalyst design principle that links material properties to the catalytic activity can accelerate the search for highly active and abundant transition-metal-oxide catalysts to replace platinum. Here, we demonstrate that the ORR activity for oxide catalysts primarily correlates to σ*-orbital (eg) occupation and the extent of B-site transition-metal–oxygen covalency, which serves as a secondary activity descriptor. Our findings reflect the critical influences of the σ* orbital and metal–oxygen covalency on the competition between O22–/OH displacement and OH regeneration on surface transition-metal ions as the rate-limiting steps of the ORR, and thus highlight the importance of electronic structure in controlling oxide catalytic activity.

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Figure 1: ORR activity of perovskite transition-metal-oxide catalysts.
Figure 2: Role of eg electron on ORR activity of perovskite oxides.
Figure 3: Proposed ORR mechanism on perovskite oxide catalysts30.
Figure 4: Role of B–O covalency on the ORR activity of perovskite oxides.

Change history

  • 17 June 2011

    In the version of this Article originally published online, the wrong descriptions for the colours of B and O atoms were given in the caption for Figure 2. This has now been corrected in all versions of the Article.


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This work was supported by Toyota Motor Company and by the DOE Hydrogen Initiative programme (award no. DE-FG02-05ER15728). The research made use of the Shared Experimental Facilities supported by the MRSEC Program of the National Science Foundation (award no. DMR 08-019762). J.S. was supported in part by the Chesonis Foundation Fellowship. J.B.G was supported by the Robert A. Welch Foundation (Houston, Texas). The authors would like to thank A. Mansour for his help with X-ray absorption spectroscopy. The National Synchrotron Light Source is supported by the US Department of Energy, Division of Material Sciences and Division of Chemical Sciences (contract no. DE-AC02-98CH10886). The beamline X11 is supported by the Office of Naval Research and contributions from Participating Research Team (PRT) members.

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Y.S.H. proposed the concept. J.S., H.A.G. and Y.S.H. designed the experiments. J.S., N.Y. and H.N. carried out the experiments. J.S., H.A.G., J.B.G. and Y.S.H. performed the analysis and wrote the manuscript.

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Correspondence to Hubert A. Gasteiger or Yang Shao-Horn.

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The authors declare no competing financial interests.

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Suntivich, J., Gasteiger, H., Yabuuchi, N. et al. Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal–air batteries. Nature Chem 3, 546–550 (2011).

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