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Analysis of the limitations in the oxygen reduction activity of transition metal oxide surfaces

Li, Hao and Kelly, Sara and Guevarra, Dan and Wang, Zhenbin and Wang, Yu and Haber, Joel A. and Anand, Megha and Gunasooriya, G. T. Kasun Kalhara and Abraham, Christina Susan and Vijay, Sudarshan and Gregoire, John M. and Nørskov, Jens K. (2021) Analysis of the limitations in the oxygen reduction activity of transition metal oxide surfaces. Nature Catalysis, 4 (6). pp. 463-468. ISSN 2520-1158. doi:10.1038/s41929-021-00618-w.

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The oxygen reduction reaction (ORR) is the key bottleneck in the performance of fuel cells. So far, the most active and stable electrocatalysts for the reaction are based on Pt group metals. Transition metal oxides (TMOs) constitute an alternative class of materials for achieving operational stability under oxidizing conditions. Unfortunately, TMOs are generally found to be less active than Pt. Here, we identify two reasons why it is difficult to find TMOs with a high ORR activity. The first is that TMO surfaces consistently bind oxygen atoms more weakly than transition metals do. This makes the breaking of the O–O bond rate-determining for the broad range of TMO surfaces investigated here. The second is that electric field effects are stronger at TMO surfaces, which further makes O–O bond breaking difficult. To validate the predictions and ascertain their generalizability for TMOs, we report experimental ORR catalyst screening for 7,798 unique TMO compositions that generally exhibit activity well below that of Pt.

Item Type:Article
Related URLs:
URLURL TypeDescription ReadCube access ItemCode
Kelly, Sara0000-0001-9424-2489
Guevarra, Dan0000-0002-9592-3195
Wang, Zhenbin0000-0002-7016-9245
Wang, Yu0000-0003-3589-9274
Haber, Joel A.0000-0001-7847-5506
Anand, Megha0000-0003-2707-3587
Gunasooriya, G. T. Kasun Kalhara0000-0003-1258-7841
Abraham, Christina Susan0000-0001-9991-0976
Vijay, Sudarshan0000-0001-8242-0161
Gregoire, John M.0000-0002-2863-5265
Nørskov, Jens K.0000-0002-4427-7728
Additional Information:© The Author(s), under exclusive licence to Springer Nature Limited 2021. Received 07 October 2020; Accepted 19 April 2021; Published 24 May 2021. We thank I. Chorkendorff, Y. Zheng (Technical University of Denmark), T. F. Jaramillo (Stanford University) and J. H. Montoya (Toyota Research Institute) for all the helpful discussions. This work was supported by the Toyota Research Institute through the Accelerated Materials Design and Discovery program. Data availability: The experimental data are available at ( The computational data, which include the O, HO and HOO binding energies, the free energies of 4e– ORR, the optimized atomic coordinates and the scripts for structure modelling, are available at All the data are available from the authors upon reasonable request. These authors contributed equally: Hao Li, Sara Kelly. Author Contributions: H.L., S.K., J.M.G. and J.K.N. designed the study and wrote the paper. H.L., S.K., Z.W., M.A., G.T.K.K.G., C.S.A. and S.V. conducted the DFT calculations, data analysis, and microkinetic modelling. D.G., Y.W., J.A.H. and J.M.G. performed the high-throughput experiments. The authors declare no competing interests. Peer review information: Nature Catalysis thanks Guofeng Wang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
Funding AgencyGrant Number
Toyota Research InstituteUNSPECIFIED
Subject Keywords:Density functional theory; Electrocatalysis; Energy; Fuel cells; Reaction kinetics and dynamics
Issue or Number:6
Record Number:CaltechAUTHORS:20210324-112501603
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Official Citation:Li, H., Kelly, S., Guevarra, D. et al. Analysis of the limitations in the oxygen reduction activity of transition metal oxide surfaces. Nat Catal 4, 463–468 (2021).
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:108544
Deposited By: Katherine Johnson
Deposited On:05 May 2021 19:51
Last Modified:12 Aug 2021 23:34

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