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Surface distortion as a unifying concept and descriptor in oxygen reduction reaction electrocatalysis


Tuning the surface structure at the atomic level is of primary importance to simultaneously meet the electrocatalytic performance and stability criteria required for the development of low-temperature proton-exchange membrane fuel cells (PEMFCs). However, transposing the knowledge acquired on extended, model surfaces to practical nanomaterials remains highly challenging. Here, we propose ‘surface distortion’ as a novel structural descriptor, which is able to reconciliate and unify seemingly opposing notions and contradictory experimental observations in regards to the electrocatalytic oxygen reduction reaction (ORR) reactivity. Beyond its unifying character, we show that surface distortion is pivotal to rationalize the electrocatalytic properties of state-of-the-art of PtNi/C nanocatalysts with distinct atomic composition, size, shape and degree of surface defectiveness under a simulated PEMFC cathode environment. Our study brings fundamental and practical insights into the role of surface defects in electrocatalysis and highlights strategies to design more durable ORR nanocatalysts.

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This work was performed within the framework of the Centre of Excellence of Multifunctional Architectured Materials ‘CEMAM’ grant number ANR-10-LABX-44-01. The authors acknowledge financial support from the Grand Equipement National de Calcul Intensif (GENCI, grant number INP2227/72914), from the French National Research Agency (grant number ANR-14-CE05-0003-01), from the Swiss National Science Foundation (grant number 20001E_151122/1), from the German Research Foundation (DFG, grant number STR 596/5-1 and EY 16/18-1), from the German Federal Ministry of Education and Research (BMBF, grant number 03SF0527A), and from the European Research Council (grant number ERC AdG 2013 AEROCAT). The authors are grateful to Dr. Gwenn Cognard and Dr. Vincent Caldeira for their contribution to the manuscript's artwork.

Author information

R.C., L.D. and F.M. conceived the experiments. R.C. carried out the experiments, analysed the data and wrote the first version of the manuscript. V.B., S.K. and L.K. contributed to materials synthesis. J.H., S.H. and T.A. contributed to electrochemical measurements. L.G. and G.R. contributed to HRTEM and STEM/X-EDS experiments. J.D. performed the WAXS experiments and P.B. the Rietveld analysis. O.L.B. and A.P. carried out the DFT calculations. All authors contributed to the discussion section and the finalization of the text and Figures of the manuscript.

Competing interests

The authors declare no competing interests.

Correspondence to Raphaël Chattot or Frédéric Maillard.

Supplementary information

Supplementary Information

Experimental Details, Supplementary Figures 1–11, Supplementary Tables 1–6, Supplementary References 1–23

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Further reading

Fig. 1: Morphological, structural and chemical characterizations of the various PtNi nanocatalysts synthesized in this study.
Fig. 2: Experimental approach used to estimate the catalysts’ structural disorder through the extraction of microstrain from the synchrotron WAXS patterns.
Fig. 3: Disentangling the contribution of chemical disorder to the values of microstrain using DFT calculations.
Fig. 4: Relationships between the kinetic current for the ORR and SD for the fresh electrocatalysts evaluated in this study.
Fig. 5: Evolution of the SD–ORR activity plot after (electro)chemical ageing.
Fig. 6: Structural and ORR activity changes under simulated PEMFC cathode environment.