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

Nature Catalysis volume 4, pages 463–468 (2021)Cite this article

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Abstract

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.

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Fig. 1: Summary of the performance of TMO catalysts.
Fig. 2: Free-energy diagram for the four-electron (4e−) ORR process on Pt, ZrO2 and HfO2(111).
Fig. 3: Linear scaling relations that determine the ORR activities.
Fig. 4: Kinetic volcano models for the 4e– ORR process at 0.8 VRHE.
Fig. 5: Electric field effects and pH-dependent kinetic volcano models.

Data availability

The experimental data are available at https://data.caltech.edu/records/1632 (https://doi.org/10.22002/D1.1632). 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 https://github.com/cattheory-oxides/data. All the data are available from the authors upon reasonable request.

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Acknowledgements

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.

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  1. These authors contributed equally: Hao Li, Sara Kelly.

Authors and Affiliations

  1. Catalysis Theory Center, Department of Physics, Technical University of Denmark, Lyngby, Denmark

    Hao Li, Zhenbin Wang, Megha Anand, G. T. Kasun Kalhara Gunasooriya, Christina Susan Abraham, Sudarshan Vijay & Jens K. Nørskov

  2. Department of Chemical Engineering, Stanford University, Stanford, CA, USA

    Sara Kelly

  3. Division of Engineering and Applied Science, California Institute of Technology, Pasadena, CA, USA

    Dan Guevarra, Yu Wang, Joel A. Haber & John M. Gregoire

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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.

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Correspondence to Jens K. Nørskov.

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Peer review information Nature Catalysis thanks Guofeng Wang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Discussion, Methods, Figs. 1–8 and References.

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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). https://doi.org/10.1038/s41929-021-00618-w

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