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


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 ( 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.


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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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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).

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