Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

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

Abstract

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.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

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.

References

  1. 1.

    Turner, J. A. Sustainable hydrogen production. Science 305, 972–974 (2004).

    Article  Google Scholar 

  2. 2.

    Eberle, D. U. & von Helmolt, D. R. Sustainable transportation based on electric vehicle concepts: a brief overview. Energy Environ. Sci. 3, 689–699 (2010).

    Article  Google Scholar 

  3. 3.

    Hansen, J. et al. Dangerous human-made interference with climate: A GISS modelE study. Atmos. Chem. Phys. 7, 2287–2312 (2007).

    Article  Google Scholar 

  4. 4.

    Steele, B. C. H. & Heinzel, A. Materials for fuel-cell technologies. Nature 414, 345–352 (2001).

    Article  Google Scholar 

  5. 5.

    Rabis, A., Rodriguez, P. & Schmidt, T. J. Electrocatalysis for polymer electrolyte fuel cells: Recent achievements and future challenges. ACS Catal. 2, 864–890 (2012).

    Article  Google Scholar 

  6. 6.

    Stamenkovic, V. R. et al. Improved oxygen reduction activity on Pt3Ni(111) via increased surface site availability. Science 315, 493–497 (2007).

    Article  Google Scholar 

  7. 7.

    Nørskov, J. K. et al. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 108, 17886–17892 (2004).

    Article  Google Scholar 

  8. 8.

    Stamenkovic, V. et al. Changing the activity of electrocatalysts for oxygen reduction by tuning the surface electronic structure. Angew. Chem. Int. Ed. 45, 2897–2901 (2006).

    Article  Google Scholar 

  9. 9.

    Paffett, M. T., Daube, K. A., Gottesfeld, S. & Campbell, C. T. Electrochemical and surface science investigations of PtCr alloy electrodes. J. Electroanal. Chem. 220, 269–285 (1987).

    Article  Google Scholar 

  10. 10.

    Bardi, U., Beard, B. C. & Ross, P. N. Surface oxidation of a Pt80Co20 alloy - An X-ray photoelectron spectroscopy and low energy electron diffraction study on the [100] and [111] oriented single crystal surfaces. J. Vac. Sci. Technol. A 6, 665–670 (1988).

    Article  Google Scholar 

  11. 11.

    Paffett, M. T., Beery, J. G. & Gottesfeld, S. Oxygen reduction at Pt0.65Cr0.35, Pt0.2Cr0.8 and roughened platinum. J. Electrochem. Soc. 135, 1431–1436 (1988).

    Article  Google Scholar 

  12. 12.

    Hammer, B. & Nørskov, J. K. Electronic factors determining the reactivity of metal surfaces. Surf. Sci. 343, 211–220 (1995).

    Article  Google Scholar 

  13. 13.

    Gauthier, Y. et al. PtxNi1−x(111) alloy surfaces: structure and composition in relation to some catalytic properties. Surf. Sci. 162, 342–347 (1985).

    Article  Google Scholar 

  14. 14.

    Bligaard, T. & Nørskov, J. K. Ligand effects in heterogeneous catalysis and electrochemistry. Electrochim. Acta 52, 5512–5516 (2007).

    Article  Google Scholar 

  15. 15.

    Hammer, B. & Nørskov, J. K. Theoretical surface science and catalysis — calculations and concepts. Adv. Catal. 45, 71–129 (2000).

  16. 16.

    Greeley, J., Nørskov, J. K. & Mavrikakis, M. Electronic structure and catalysis on metal surfaces. Annu. Rev. Phys. Chem. 53, 319–348 (2002).

    Article  Google Scholar 

  17. 17.

    Cui, C., Gan, L., Heggen, M., Rudi, S. & Strasser, P. Compositional segregation in shaped Pt alloy nanoparticles and their structural behaviour during electrocatalysis. Nat. Mater. 12, 765–771 (2013).

    Article  Google Scholar 

  18. 18.

    Beermann, V. et al. Rh-doped Pt-Ni octahedral nanoparticles: Understanding the correlation between elemental distribution, oxygen reduction reaction, and shape stability. Nano Lett. 16, 1719–1725 (2016).

    Article  Google Scholar 

  19. 19.

    Beermann, V. et al. Tuning the electrocatalytic oxygen reduction reaction activity and stability of shape-controlled Pt-Ni nanoparticles by thermal annealing - Elucidating the surface atomic structural and compositional changes. J. Am. Chem. Soc. 139, 16536–16547 (2017).

    Article  Google Scholar 

  20. 20.

    Van Der Niet, M. J. T. C., Garcia-Araez, N., Hernández, J., Feliu, J. M. & Koper, M. T. M. Water dissociation on well-defined platinum surfaces: The electrochemical perspective. Catal. Today 202, 105–113 (2013).

    Article  Google Scholar 

  21. 21.

    Farias, M. J. S., Camara, G. A. & Feliu, J. M. Understanding the CO preoxidation and the intrinsic catalytic activity of step sites in stepped Pt surfaces in acidic medium. J. Phys. Chem. C. 119, 20272–20282 (2015).

    Article  Google Scholar 

  22. 22.

    Gómez-Marín, A. M. & Feliu, J. M. Oxygen reduction on nanostructured platinum surfaces in acidic media: Promoting effect of surface steps and ideal response of Pt(111). Catal. Today 244, 172–176 (2015).

    Article  Google Scholar 

  23. 23.

    Sugimura, F., Nakamura, M. & Hoshi, N. The oxygen reduction reaction on kinked stepped surfaces of Pt. Electrocatalysis 8, 46–50 (2017).

    Article  Google Scholar 

  24. 24.

    Calle-Vallejo, F. et al. Finding optimal surface sites on heterogeneous catalysts by counting nearest neighbors. Science 350, 185–190 (2015).

    Article  Google Scholar 

  25. 25.

    Calle-Vallejo, F., Pohl, M. D. & Bandarenka, A. S. Quantitative coordination-activity relations for the design of enhanced Pt catalysts for CO electro-oxidation. ACS Catal. 7, 4355–4359 (2017).

    Article  Google Scholar 

  26. 26.

    Dubau, L. et al. Defects do catalysis: CO monolayer oxidation and oxygen reduction reaction on hollow PtNi/C nanoparticles. ACS Catal. 6, 4673–4684 (2016).

    Article  Google Scholar 

  27. 27.

    Li, M. et al. Ultrafine jagged platinum nanowires enable ultrahigh mass activity for the oxygen reduction reaction. Science 354, 1414–1419 (2016).

    Article  Google Scholar 

  28. 28.

    Chattot, R. et al. Beyond strain and ligand effects: Microstrain-induced enhancement of the oxygen reduction reaction kinetics on various PtNi/C nanostructures. ACS Catal. 7, 398–408 (2017).

    Article  Google Scholar 

  29. 29.

    Calle-Vallejo, F. et al. Why conclusions from platinum model surfaces do not necessarily lead to enhanced nanoparticle catalysts for the oxygen reduction reaction. Chem. Sci. 8, 2283–2289 (2017).

    Article  Google Scholar 

  30. 30.

    Langford, J. I. & Lou, D. Powder diffraction. Rep. Prog. Phys. 59, 131–234 (1996).

    Article  Google Scholar 

  31. 31.

    Stukowski, A., Markmann, J., Weissmüller, J. & Albe, K. Atomistic origin of microstrain broadening in diffraction data of nanocrystalline solids. Acta Mater. 57, 1648–1654 (2009).

    Article  Google Scholar 

  32. 32.

    Kurlov, A. S. & Gusev, A. I. Determination of the particle sizes, microstrains, and degree of inhomogeneity in nanostructured materials from X-ray diffraction data. Glas. Phys. Chem. 33, 276–282 (2007).

    Article  Google Scholar 

  33. 33.

    Le Bacq, O. et al. Effect of atomic vacancies on the structure and the electrocatalytic activity of Pt-rich/C nanoparticles: A combined experimental and density functional theory study. ChemCatChem 9, 2324–2338 (2017).

    Article  Google Scholar 

  34. 34.

    Montejano-Carrizales, J. M., Aguilera-Granja, F. & Morán-López, J. L. Direct enumeration of the geometrical characteristics of clusters. Nanostruct. Mater. 8, 269–287 (1997).

    Article  Google Scholar 

  35. 35.

    Montejano-Carrizales, J. M. & Morán-López, J. L. Geometrical characteristics of compact nanoclusters. Nanostruct. Mater. 1, 397–409 (1992).

    Article  Google Scholar 

  36. 36.

    Gan, L., Rudi, S., Cui, C., Heggen, M. & Strasser, P. Size-controlled synthesis of sub-10 nm PtNi3 alloy nanoparticles and their unusual volcano-shaped size effect on ORR electrocatalysis. Small 12, 3189–3196 (2016).

    Article  Google Scholar 

  37. 37.

    Gan, L., Cui, C., Rudi, S. & Strasser, P. Core-shell and nanoporous particle architectures and their effect on the activity and stability of Pt ORR electrocatalysts. Top. Catal. 57, 236–244 (2014).

    Article  Google Scholar 

  38. 38.

    Strasser, P. et al. Lattice-strain control of the activity in dealloyed core–shell fuel cell catalysts. Nat. Chem. 2, 454–460 (2010).

    Article  Google Scholar 

  39. 39.

    Grammatikopoulos, P., Cassidy, C., Singh, V. & Sowwan, M. Coalescence-induced crystallisation wave in Pd nanoparticles. Sci. Rep. 4, 5779 (2014).

    Article  Google Scholar 

  40. 40.

    Asset, T. et al. Elucidating the mechanisms driving the aging of porous hollow PtNi/C nanoparticles by means of COads stripping. ACS Appl. Mater. Interfaces 9, 25298–25307 (2017).

  41. 41.

    Kitchin, J. R., Nørskov, J. K., Barteau, M. A. & Chen, J. G. Role of strain and ligand effects in the modification of the electronic and chemical properties of bimetallic surfaces. Phys. Rev. Lett. 93, 4–7 (2004).

    Article  Google Scholar 

  42. 42.

    Kienitz, B., Pivovar, B., Zawodzinski, T. & Garzon, F. H. Cationic contamination effects on polymer electrolyte membrane fuel cell performance. J. Electrochem. Soc. 158, B1175–B1183 (2011).

    Article  Google Scholar 

  43. 43.

    Gan, L., Heggen, M., Rudi, S. & Strasser, P. Core–shell compositional fine structures of dealloyed PtxNi1−x nanoparticles and their impact on oxygen reduction catalysis. Nano Lett. 12, 5423–5430 (2012).

    Article  Google Scholar 

  44. 44.

    Oezaslan, M., Hasché, F. & Strasser, P. Pt-based core–shell catalyst architectures for oxygen fuel cell electrodes. J. Phys. Chem. Lett. 4, 3273–3291 (2013).

    Article  Google Scholar 

  45. 45.

    Zhang, J., Yang, H., Fang, J. & Zou, S. Synthesis and oxygen reduction activity of shape-controlled Pt3Ni nanopolyhedra. Nano Lett. 10, 638–644 (2010).

    Article  Google Scholar 

  46. 46.

    Bae, S. J. et al. Facile preparation of carbon-supported PtNi hollow nanoparticles with high electrochemical performance. J. Mater. Chem. 22, 8820–8825 (2012).

    Article  Google Scholar 

  47. 47.

    Henning, S. et al. Pt-Ni aerogels as unsupported electrocatalysts for the oxygen reduction reaction. J. Electrochem. Soc. 163, F998–F1003 (2016).

    Article  Google Scholar 

  48. 48.

    Ashiotis, G. et al. The fast azimuthal integration Python library: PyFAI. J. Appl. Crystallogr. 48, 510–519 (2015).

    Article  Google Scholar 

  49. 49.

    Rodríguez-Carvajal, J. Recent advances in magnetic structure determination by neutron powder diffraction. Phys. B Condens. Matter 192, 55–69 (1993).

    Article  Google Scholar 

  50. 50.

    Thompson, P., Cox, D. E. & Hastings, J. B. Rietveld refinement of Debye–Scherrer synchrotron X-ray data from Al2O3. J. Appl. Crystallogr. 20, 79–83 (1987).

    Article  Google Scholar 

Download references

Acknowledgements

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

Affiliations

Authors

Contributions

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.

Corresponding authors

Correspondence to Raphaël Chattot or Frédéric Maillard.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

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

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Chattot, R., Le Bacq, O., Beermann, V. et al. Surface distortion as a unifying concept and descriptor in oxygen reduction reaction electrocatalysis. Nature Mater 17, 827–833 (2018). https://doi.org/10.1038/s41563-018-0133-2

Download citation

Further reading

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing