Skip to main content

Thank you for visiting 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.

Self-supported Pt–CoO networks combining high specific activity with high surface area for oxygen reduction


Several concepts for platinum-based catalysts for the oxygen reduction reaction (ORR) are presented that exceed the US Department of Energy targets for Pt-related ORR mass activity. Most concepts achieve their high ORR activity by increasing the Pt specific activity at the expense of a lower electrochemically active surface area (ECSA). In the potential region controlled by kinetics, such a lower ECSA is counterbalanced by the high specific activity. At higher overpotentials, however, which are often applied in real systems, a low ECSA leads to limitations in the reaction rate not by kinetics, but by mass transport. Here we report on self-supported platinum–cobalt oxide networks that combine a high specific activity with a high ECSA. The high ECSA is achieved by a platinum–cobalt oxide bone nanostructure that exhibits unprecedentedly high mass activity for self-supported ORR catalysts. This concept promises a stable fuel-cell operation at high temperature, high current density and low humidification.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Fig. 1: HAADF STEM and SEM images of self-supported nanoporous Pt–CoO networks.
Fig. 2: Comparison of ORR performance at 0.9 VRHE for different standard and model catalysts with the best-performing NP Pt–CoO network.
Fig. 3: Ex situ and in situ XAS analysis.
Fig. 4: X-Ray total scattering.
Fig. 5: Comparison of ORR MAs.

Data availability

The data supporting the findings of this study are available within this article and its Supplementary Information, or from the corresponding author upon reasonable request. Source data are provided with this paper.

Code availability

The X-ray total scattering analysis and modelling were done in PDFgetX3 and PDFgui. The fitting parameters can be found in the Supplementary Information. The XAS data were analysed by using the IFEFFIT software. DFT calculations were performed with Gpaw and ASE, which are open source codes. The structure and script can be found on the website of the Department of Chemistry, University of Copenhagen.


  1. 1.

    Banham, D. W. H. & Ye, S. Current status and future development of catalyst materials and catalyst layers for PEMFCs: an industrial perspective. ACS Energy Lett. 2, 629–638 (2017).

    CAS  Google Scholar 

  2. 2.

    Chattot, R. et al. Surface distortion as a unifying concept and descriptor in oxygen reduction reaction electrocatalysis. Nat. Mater. 17, 827–833 (2018).

    CAS  Google Scholar 

  3. 3.

    Stamenkovic, V. R. et al. Trends in electrocatalysis on extended and nanoscale Pt–bimetallic alloy surfaces. Nat. Mater. 6, 241–247 (2007).

    CAS  Google Scholar 

  4. 4.

    Chen, C. et al. Highly crystalline multimetallic nanoframes with three-dimensional electrocatalytic surfaces. Science. 343, 1339–1343 (2014).

    CAS  Google Scholar 

  5. 5.

    Zhang, L. et al. Platinum-based nanocages with subnanometer-thick walls and well-defined, controllable facets. Science 349, 412–416 (2015).

    CAS  Google Scholar 

  6. 6.

    Choi, S.-I. et al. Synthesis and characterization of 9 nm Pt–Ni octahedra with a record high activity of 3.3 A/mg Pt for the oxygen reduction reaction. Nano Lett. 13, 3420–3425 (2013).

    CAS  Google Scholar 

  7. 7.

    Velázquez-Palenzuela, A. et al. The enhanced activity of mass-selected PtxGd nanoparticles for oxygen electroreduction. J. Catal. 328, 297–307 (2015).

    Google Scholar 

  8. 8.

    Debe, M. K. Electrocatalyst approaches and challenges for automotive fuel cells. Nature 486, 43–51 (2012).

    CAS  Google Scholar 

  9. 9.

    Liu, W. et al. Noble metal aerogels—synthesis, characterization, and application as electrocatalysts. Acc. Chem. Res. 48, 154–162 (2015).

    CAS  Google Scholar 

  10. 10.

    Stephens, I., Bondarenko, A., U, G., Rossmeisl, J. & Chorkendorff, I. Understanding the electrocatalysis of oxygen reduction on platinum and its alloys. Energy 5, 6744–6762 (2012).

    CAS  Google Scholar 

  11. 11.

    Escudero-Escribano, M., Jensen, K. D. & Jensen, A. W. Recent advances in bimetallic electrocatalysts for oxygen reduction: design principles, structure–function relations and active phase elucidation. Curr. Opin. Electrochem. 8, 135–146 (2018).

    CAS  Google Scholar 

  12. 12.

    Escudero-Escribano, M. et al. Tuning the activity of Pt alloy electrocatalysts by means of the lanthanide contraction. Science 352, 73–76 (2016).

    CAS  Google Scholar 

  13. 13.

    Zalitis, C. M., Kramer, D. & Kucernak, A. R. Electrocatalytic performance of fuel cell reactions at low catalyst loading and high mass transport. Phys. Chem. Chem. Phys. 15, 4329–4340 (2013).

    CAS  Google Scholar 

  14. 14.

    Inaba, M. et al. Benchmarking high surface area electrocatalysts in a gas diffusion electrode: measurement of oxygen reduction activities under realistic conditions. Energy Environ. Sci. 11, 988–994 (2018).

    CAS  Google Scholar 

  15. 15.

    Kongkanand, A. & Mathias, M. F. The Priority and Challenge of High-Power Performance of Low-Platinum Proton-Exchange Membrane Fuel Cells. J. Phys. Chem. Lett. 7, 1127–1137 (2016).

    CAS  Google Scholar 

  16. 16.

    Costentin, C., Di Giovanni, C., Giraud, M., Savéant, J. M. & Tard, C. Nanodiffusion in electrocatalytic films. Nat. Mater. 16, 1016–1021 (2017).

    CAS  Google Scholar 

  17. 17.

    Ott, S. et al. Ionomer distribution control in porous carbon-supported catalyst layers for high-power and low Pt-loaded proton exchange membrane fuel cells. Nat. Mater. (2019).

    Article  Google Scholar 

  18. 18.

    Orfanidi, A., Rheinländer, P. J., Schulte, N. & Gasteiger, H. A. Ink solvent dependence of the ionomer distribution in the catalyst layer of a PEMFC. J. Electrochem. Soc. 165, F1254–F1263 (2018).

    CAS  Google Scholar 

  19. 19.

    Jensen, A. W. et al. Self-supported nanostructured iridium-based networks as highly active electrocatalysts for oxygen evolution in acidic media. J. Mater. Chem. A 8, 1066–1071 (2020).

    CAS  Google Scholar 

  20. 20.

    Sievers, G., Bowen, J. R., Brüser, V. & Arenz, M. Support-free nanostructured Pt–Cu electrocatalyst for the oxygen reduction reaction prepared by alternating magnetron sputtering. J. Power Sources 413, 432–440 (2019).

    CAS  Google Scholar 

  21. 21.

    Gasteiger, H. A., Kocha, S. S., Sompalli, B. & Wagner, F. T. Activity benchmarks and requirements for Pt, Pt–alloy, and non-Pt oxygen reduction catalysts for PEMFCs. Appl. Catal. B 56, 9–35 (2005).

    CAS  Google Scholar 

  22. 22.

    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).

    Google Scholar 

  23. 23.

    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).

    CAS  Google Scholar 

  24. 24.

    Zana, A., Speder, J., Reeler, N. E. A., Vosch, T. & Arenz, M. Investigating the corrosion of high surface area carbons during start/stop fuel cell conditions: a Raman study. Electrochim. Acta 114, 455–461 (2013).

    CAS  Google Scholar 

  25. 25.

    Zana, A. et al. Probing degradation by IL-TEM: the influence of stress test conditions on the degradation mechanism. J. Electrochem. Soc. 160, F608–F615 (2013).

    CAS  Google Scholar 

  26. 26.

    Wang, C. et al. Monodisperse Pt3Co nanoparticles as a catalyst for the oxygen reduction reaction: size-dependent activity. J. Phys. Chem. C 113, 19365–19368 (2009).

    CAS  Google Scholar 

  27. 27.

    Debe, M. K. Tutorial on the fundamental characteristics and practical properties of nanostructured thin film (NSTF) catalysts. J. Electrochem. Soc. 160, F522–F534 (2013).

    CAS  Google Scholar 

  28. 28.

    Hernandez-Fernandez, P. et al. Mass-selected nanoparticles of PtxY as model catalysts for oxygen electroreduction. Nat. Chem. 6, 732–738 (2014).

    CAS  Google Scholar 

  29. 29.

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

    CAS  Google Scholar 

  30. 30.

    Zeng, Z., Chang, K. C., Kubal, J., Markovic, N. M. & Greeley, J. Stabilization of ultrathin (hydroxy)oxide films on transition metal substrates for electrochemical energy conversion. Nat. Energy 2, 17070 (2017).

    CAS  Google Scholar 

  31. 31.

    Chatti, M. et al. Intrinsically stable in situ generated electrocatalyst for long-term oxidation of acidic water at up to 80 °C. Nat. Catal. 2, 457–465 (2019).

    CAS  Google Scholar 

  32. 32.

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

    CAS  Google Scholar 

  33. 33.

    Sievers, G., Jensen, A. W., Brüser, V., Arenz, M. & Escudero-Escribano, M. Sputtered platinum thin-films for oxygen reduction in gas diffusion electrodes: a model system for studies under realistic reaction conditions. Surfaces 2, 336–348 (2019).

    CAS  Google Scholar 

  34. 34.

    Suzuki, T. et al. Toward the Future Fuel Cell—Challenge for 2040. ECS Trans. 92, 3–7 (2019).

    CAS  Google Scholar 

  35. 35.

    Nesselberger, M. et al. The particle size effect on the oxygen reduction reaction activity of Pt catalysts: influence of electrolyte and relation to single crystal models. J. Am. Chem. Soc. 133, 17428–17433 (2011).

    CAS  Google Scholar 

  36. 36.

    Spanos, I., Kirkensgaard, J. J. K., Mortensen, K. & Arenz, M. Investigating the activity enhancement on PtxCo1−x alloys induced by a combined strain and ligand effect. J. Power Sources 245, 908–914 (2014).

    CAS  Google Scholar 

  37. 37.

    Bu, L. et al. Surface engineering of hierarchical platinum–cobalt nanowires for efficient electrocatalysis. Nat. Commun. 7, 11850 (2016).

    CAS  Google Scholar 

  38. 38.

    Huang, X. et al. High-performance transition metal-doped Pt3Ni octahedra for oxygen reduction reaction. Science 348, 1230–1234 (2015).

    CAS  Google Scholar 

  39. 39.

    Chong, L. et al. Ultralow-loading platinum–cobalt fuel cell catalysts derived from imidazolate frameworks. Science 1281, 1276–1281 (2018).

    Google Scholar 

  40. 40.

    Bu, L. et al. Biaxially strained PtPb/Pt core/shell nanoplate boosts oxygen reduction catalysis. Science 354, 1410–1414 (2016).

    CAS  Google Scholar 

  41. 41.

    Xu, S. et al. Extending the limits of Pt/C catalysts with passivation-gas-incorporated atomic layer deposition. Nat. Catal. 1, 624–630 (2018)

    CAS  Google Scholar 

  42. 42.

    Liu, W. et al. Bimetallic aerogels: high-performance electrocatalysts for the oxygen reduction reaction. Angew. Chem. Int. Ed. 52, 9849–9852 (2013).

    CAS  Google Scholar 

  43. 43.

    Mayrhofer, K. J. J., Ashton, S. J., Kreuzer, J. & Arenz, M. An electrochemical cell configuration incorporating an ion conducting membrane separator between reference and working electrode. Int. J. Electrochem. Sci. 4, 1–8 (2009).

    CAS  Google Scholar 

  44. 44.

    Kalliat, M., Kwak, C. & Schmidt, P. in New approaches in coal chemistry (eds Blaustein, D., Bockrathand, B. & Friedman, S.) 3–22 (American Chemical Society, 1981).

  45. 45.

    Newville, M. IFEFFIT: interactive XAFS analysis and FEFF fitting. J. Synchrotron Radiat. 8, 322–324 (2001).

    CAS  Google Scholar 

  46. 46.

    Chupas, P. J. et al. Rapid-acquisition pair distribution function (RA-PDF) analysis. J. Appl. Crystallogr. 36, 1342–1347 (2003).

    CAS  Google Scholar 

  47. 47.

    Juhás, P., Farrow, C. L., Yang, X., Knox, K. R. & Billinge, S. J. L. Complex modeling: a strategy and software program for combining multiple information sources to solve ill posed structure and nanostructure inverse problems. Acta Crystallogr. A 71, 562–568 (2015).

    Google Scholar 

  48. 48.

    Farrow, C. L. et al. PDFfit2 and PDFgui: Computer programs for studying nanostructure in crystals. J. Phys. Condens. Matter 19, 33 (2007).

    Google Scholar 

Download references


This work was supported by the Danish DFF through grant no. 4184-00332, the Villum Center for the Science of Sustainable Fuels and Chemicals (grant no. 9455) and the Danish National Research Foundation Center for High-Entropy Alloys Catalysis (CHEAC). M.A. acknowledges funding from the Swiss National Science Foundation (SNSF) via project no. 200021_184742. G.W.S. and V.B. acknowledge support from BMBF for funding the validation (VIP+) project 3DnanoMe (FKZ 03VP06451). The authors acknowledge the collaboration with L. T. Kuhn and S. B. Simonsen concerning TEM measurements, A. Mingers for ICP-MS measurements, G. Cibin, S. Belin and M. Nachtegal for technical support at the Quick EXAFS beam line, B18, Diamond Light Source (DLS), the ROCK beam line (proposal ID 20180795) of Synchrotron SOLEIL and the Super XAS beamline, X10DA, of the Swiss light source (SLS) of the Paul Scherrer Institute, respectively. The work at the ROCK beamline was supported by a public grant overseen by the French National Research Agency (ANR) as part of the ‘Investissements d’Avenir’ programme (reference ANR10-EQPX45). A.D. and M.O. received funding from the DFG (FOR2213, TP9) and the Federal Ministry of Education and Research (BMBF, ECatPEMFC, FKZ 03SF0539). K.M.Ø.J. and M.J. are grateful to the Villum Foundation for financial support through a Villum Young Investigator grant (VKR00015416). We furthermore thank DANSCATT (supported by the Danish Agency for Science and Higher Education) for support. This research used resources at the Advanced Photon Source, a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract no. DE-AC02-06CH11357.

Author information




G.W.S. and M.A. designed and proposed the research direction, analysed the results and drafted and wrote the paper. G.W.S. performed and analysed electrochemical, XAS, SEM, TEM and EDX measurements as well as plasma technical experiments. A.W.J. designed, performed and analysed the electrochemical experiments and co-wrote the paper. J.Q. collected and analysed SAXS, XAS and TEM data and co-wrote the paper. A.Z. helped acquire, analyse and interpret ex situ and in situ XAS measurements and electrochemical measurements. F.B. performed electrochemical measurements and XAS data. M.O. collected and analysed XAS data and co-wrote the paper. A.D. acquired and analysed XAS data. J.J.K.K. acquired and analysed SAXS data. T.E.L.S. and S.K. acquired and analysed STEM tomography. M.J. and K.M.Ø.J. acquired, analysed and interpreted the PDF data. K.A. and V.B. contributed to the planning, execution and interpretation of plasma technical experiments. H.W. and J.R. executed the DFT calculations, interpretation of the data and co-wrote the paper. J.S. and K. Č. acquired and analysed the HAADF STEM elemental distribution and co-wrote the paper. M.E.-E. interpreted the electrochemical data and co-wrote the paper. A.Q. acquired, analysed and interpreted the XPS experiments. All the authors discussed the results and participated in writing the manuscript.

Corresponding authors

Correspondence to Gustav W. Sievers or Matthias Arenz.

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

Supplementary Tables 1–5, Figs. 1–23 and refs. 1–12.

Supplementary Video 1

STEM tomography.

Supplementary Video 2

STEM tomography.

Supplementary Video 3

STEM tomography.

Source data

Source Data Fig. 2

Graph source data.

Source Data Fig. 3

Graph source data.

Source Data Fig. 4

Graph source data.

Source Data Fig. 5

Graph source data.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Sievers, G.W., Jensen, A.W., Quinson, J. et al. Self-supported Pt–CoO networks combining high specific activity with high surface area for oxygen reduction. Nat. Mater. 20, 208–213 (2021).

Download citation

Further reading


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