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.
This is a preview of subscription content
Subscription info for Chinese customers
We have a dedicated website for our Chinese customers. Please go to naturechina.com to subscribe to this journal.
Get time limited or full article access on ReadCube.
All prices are NET prices.
Gasteiger, H. A. & Markovic, N. M. Just a dream-or future reality? Science 324, 48–49 (2009).
Whitesides, G. M. & Crabtree, G. W. Don't forget long-term fundamental research in energy. Science 315, 796–798 (2007).
Gray, H. B. Powering the planet with solar fuel. Nature Chem. 1, 7 (2009).
Lewis, N. S. & Nocera, D. G. Powering the planet: chemical challenges in solar energy utilization. Proc. Natl Acad. Sci. USA 103, 15729–15735 (2006).
Kanan, M. W. & Nocera, D. G. In situ formation of an oxygen-evolving catalyst in neutral water containing phosphate and Co2+. Science 321, 1072–1075 (2008).
Service, R. F. Transportation research hydrogen cars: fad or the future? Science 324, 1257–1259 (2009).
Armand, M. & Tarascon, J. M. Building better batteries. Nature 451, 652–657 (2008).
Lu, Y. C. et al. Platinum–gold nanoparticles: a highly active bifunctional electrocatalyst for rechargeable lithium–air batteries. J. Am. Chem. Soc. 132, 12170–12171 (2010).
Norskov, J. K. et al. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 108, 17886–17892 (2004).
Stamenkovic, V. R. et al. Improved oxygen reduction activity on Pt3Ni(111) via increased surface site availability. Science 315, 493–497 (2007).
Stamenkovic, V. R. et al. Changing the activity of electrocatalysts for oxygen reduction by tuning the surface electronic structure. Angew. Chem. Int. Ed. 45, 2897–2901 (2006).
Lima, F. H. B. et al. Catalytic activity d-band center correlation for the O2 reduction reaction on platinum in alkaline solutions. J. Phys. Chem. C 111, 404–410 (2007).
Greeley, J. et al. Alloys of platinum and early transition metals as oxygen reduction electrocatalysts. Nature Chem. 1, 552–556 (2009).
Meadowcroft, D. B. Low-cost oxygen electrode material. Nature 226, 847–848 (1970).
Suntivich, J., Gasteiger, H. A., Yabuuchi, N. & Shao-horn, Y. Electrocatalytic measurement methodology of oxide catalysts using a thin-film rotating disk electrode. J. Electrochem. Soc. 157, B1263–B1268 (2010).
Bockris, J. O. & Otagawa, T. The electrocatalysis of oxygen evolution on perovskites. J. Electrochem. Soc. 131, 290–302 (1984).
Zou, Z. G., Ye, J. H., Sayama, K. & Arakawa, H. Direct splitting of water under visible light irradiation with an oxide semiconductor photocatalyst. Nature 414, 625–627 (2001).
Matsumoto, Y., Yoneyama, H. & Tamura, H. Influence of nature of conduction-band of transition-metal oxides on catalytic activity for oxygen reduction. J. Electroanal. Chem. 83, 237–243 (1977).
Matsumoto, Y., Yoneyama, H. & Tamura, H., Catalytic activity for electrochemical reduction of oxygen of lanthanum nickel-oxide and related oxides. J. Electroanal. Chem. 79, 319–326 (1977).
Matsumoto, Y., Yoneyama, H. & Tamura, H. A new catalyst for cathodic reduction of oxygen: lanthanum nickel oxide. Chem. Lett. 661–662 (1975).
Bockris, J. O. & Otagawa, T. Mechanism of oxygen evolution on perovskites. J. Phys. Chem. 87, 2960–2971 (1983).
Morin, F. J. & Wolfram, T. Surface states and catalysis on d-band perovskites. Phys. Rev. Lett. 30, 1214–1217 (1973).
Goodenough, J. B. & Zhou, J. S. in Localized to Itinerant Electronic Transition in Perovskite Oxides Vol. 98, 17–113 (Springer-Verlag Berlin, 2001).
Yan, J. Q., Zhou, J. S. & Goodenough, J. B. Ferromagnetism in LaCoO3 . Phys. Rev. B 70, 014402 (2004).
Markovic, N. M., Gasteiger, H. A. & Ross, P. N. Oxygen reduction on platinum low-index single-crystal surfaces in alkaline solution: rotating ring disk (Pt(hkl)) studies. J. Phys. Chem. 100, 6715–6721 (1996).
Fernandez, E. M. et al. Scaling relationships for adsorption energies on transition metal oxide, sulfide, and nitride surfaces. Angew. Chem. Int. Ed. 47, 4683–4686 (2008).
Tejuca, L. G., Fierro, J. L. G. & Tascon, J. M. D. Structure and reactivity of perovskite-type oxides. Adv. Catal. 36, 237–328 (1989).
Dowden, D. A. Crystal and ligand field models of solid catalysts. Catal. Rev. 5, 1–32 (1971).
Yokoi, Y. & Uchida, H. Catalytic activity of perovskite-type oxide catalysts for direct decomposition of NO: correlation between cluster model calculations and temperature-programmed desorption experiments. Catal. Today 42, 167–174 (1998).
Goodenough, J. B. & Cushing, B. L., in Handbook of Fuel Cells — Fundamentals, Technology and Applications Vol. 2, 520–533 (eds Vielstich, W., Gasteiger, H. A. & Yokokawa, H. (Wiley, 2003).
Abbate, M. et al. Probing depth of surface X-ray absorption spectroscopy measured in total electron-yield-mode. Surf. Interface Anal. 18, 65–69 (1992).
Abbate, M. et al. Controlled-valence properties of La1–xSrxFeO3 and La1–xSrxMnO3 studied by soft-X-ray absorption-spectroscopy. Phys. Rev. B 46, 4511–4519 (1992).
Rossmeisl, J., Qu, Z. W., Zhu, H., Kroes, G. J. & Norskov, J. K. Electrolysis of water on oxide surfaces. J. Electroanal. Chem. 607, 83–89 (2007).
Gasteiger, H. A., Kocha, S. S., Sompalli, B. & Wagner, F. T. Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs. Appl. Catal. B 56, 9–35 (2005).
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.
The authors declare no competing financial interests.
About this article
Cite this article
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). https://doi.org/10.1038/nchem.1069
Electrode reconstruction strategy for oxygen evolution reaction: maintaining Fe-CoOOH phase with intermediate-spin state during electrolysis
Nature Communications (2022)
Reversely trapping atoms from a perovskite surface for high-performance and durable fuel cell cathodes
Nature Catalysis (2022)
Oxygen Evolution Reaction in Energy Conversion and Storage: Design Strategies Under and Beyond the Energy Scaling Relationship
Nano-Micro Letters (2022)
Exsolution of CoFe(Ru) nanoparticles in Ru-doped (La0.8Sr0.2)0.9Co0.1Fe0.8Ru0.1O3−δ for efficient oxygen evolution reaction
Nano Research (2022)
Topics in Catalysis (2022)