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

Abstract

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.

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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.

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Acknowledgements

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.

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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.

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Correspondence to Gustav W. Sievers or Matthias Arenz.

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Supplementary information

Supplementary Information

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

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STEM tomography.

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STEM tomography.

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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). https://doi.org/10.1038/s41563-020-0775-8

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