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Rational strain engineering in delafossite oxides for highly efficient hydrogen evolution catalysis in acidic media

Nature Catalysis volume 3, pages 55–63 (2020)Cite this article

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Abstract

The rational design of hydrogen evolution reaction electrocatalysts that can compete with platinum is an outstanding challenge in the process of designing viable power-to-gas technologies. Here, we introduce delafossites as a family of hydrogen evolution reaction electrocatalysts in acidic media. We show that, in PdCoO2, the inherently strained Pd metal sublattice acts as a pseudomorphic template for the growth of a tensile-strained Pd-rich capping layer under reductive conditions. The surface modification ranges up to 400 nm and continuously improves the electrocatalytic activity by simultaneously increasing the exchange current density and by reducing the Tafel slope down to 38 mV dec−1, leading to overpotentials η10 < 15 mV. The improved activity is attributed to the operando stabilization of a β-PdHx phase with enhanced surface catalytic properties with respect to pure or nanostructured palladium. These findings illustrate how operando-induced electrodissolution can be used as a top-down design concept through the strain-stabilized formation of catalytically active phases.

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Fig. 1: Crystal structure of the delafossites and the evolution of the electrochemical activity for HER.
Fig. 2: Surface modifications on the delafossites before and after electrocatalytic HER in 1 M H2SO4.
Fig. 3: XPS spectra.
Fig. 4: STEM analysis of the Pd capping layer on PdCoO2.

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The data supporting the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

We gratefully acknowledge P. Schützendübe and M. Wieland for the XPS measurements, and E. Frau and P. Iyengar for the introduction to and assistance with the SECM measurements. Y. Eren Suyolcu, A. Bandarenka, N. Vargas-Barbosa, and especially R. Merkle are acknowledged for fruitful discussions. We further acknowledge C. Hohmann (NIM) for creating the figure in the table of contents. E.A.-L. acknowledges support from the SNF Ambizione Energy programme and the research programme of FOM, which is financially supported by the Netherlands Organisation for Scientific Research (NWO). S.Z. and C.S. acknowledge financial support from the German Research Foundation (DFG) under the priority programme SPP 1613 (DFG SCHE 634/12-2). B.V.L. acknowledges the Cluster of Excellence e-conversion. F.P., E.A.-L., B.V.L. and A.F.i.M. thank the MPS-EPFL Center for financial and logistic support.

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Authors and Affiliations

  1. Max Planck Institute for Solid State Research, Stuttgart, Germany

    Filip Podjaski, Daniel Weber, Leo Diehl, Roland Eger, Viola Duppel, Frederik Haase & Bettina V. Lotsch

  2. Laboratory of Semiconductor Materials, Institute of Materials, Faculty of Engineering, École Polytechnique Fédérale de Lausanne, Lausanne, Switzerland

    Filip Podjaski & Anna Fontcuberta i Morral

  3. Department of Chemistry, Ludwig Maximilian University of Munich, Munich, Germany

    Daniel Weber, Leo Diehl, Frederik Haase & Bettina V. Lotsch

  4. Max-Planck-Institut für Eisenforschung, Düsseldorf, Germany

    Siyuan Zhang & Christina Scheu

  5. AMOLF, Amsterdam, the Netherlands

    Esther Alarcón-Lladó

  6. Max Planck Institute for Intelligent Systems, Stuttgart, Germany

    Gunther Richter

  7. Institute of Physics, Faculty of Basic Sciences, École Polytechnique Fédérale de Lausanne, Lausanne, Switzerland

    Anna Fontcuberta i Morral

  8. Cluster of Excellence e-conversion, Munich, Germany

    Bettina V. Lotsch

  9. Center for Nanoscience, Munich, Germany

    Bettina V. Lotsch

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  1. Filip Podjaski
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Contributions

F.P., D.W., F.H. and B.V.L. conceived the project and the contributing measurements. The materials were synthesized by D.W., L.D. and R.E. All sample preparation and electrochemical measurements were done by F.P. The SECM data were analysed and discussed by E.A.-L. and F.P. G.R. and F.P. analysed the XPS data. S.Z. performed the STEM experiments, including the data analysis and presentation. F.P. created all of the other graphs. F.P. and B.V.L. wrote the manuscript. All authors, including V.D., C.S. and A.F.iM. contributed to discussion of the measurements, data interpretation and manuscript preparation.

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Correspondence to Bettina V. Lotsch.

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Supplementary Figs. 1–16, Tables 1–6, Notes 1–6 and references.

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Podjaski, F., Weber, D., Zhang, S. et al. Rational strain engineering in delafossite oxides for highly efficient hydrogen evolution catalysis in acidic media. Nat Catal 3, 55–63 (2020). https://doi.org/10.1038/s41929-019-0400-x

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