Article

Stabilization of ultrathin (hydroxy)oxide films on transition metal substrates for electrochemical energy conversion

  • Nature Energy volume 2, Article number: 17070 (2017)
  • doi:10.1038/nenergy.2017.70
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Abstract

Design of cost-effective electrocatalysts with enhanced stability and activity is of paramount importance for the next generation of energy conversion systems, including fuel cells and electrolysers. However, electrocatalytic materials generally improve one of these properties at the expense of the other. Here, using density functional theory calculations and electrochemical surface science measurements, we explore atomic-level features of ultrathin (hydroxy)oxide films on transition metal substrates and demonstrate that these films exhibit both excellent stability and activity for electrocatalytic applications. The films adopt structures with stabilities that significantly exceed bulk Pourbaix limits, including stoichiometries not found in bulk and properties that are tunable by controlling voltage, film composition, and substrate identity. Using nickel (hydroxy)oxide/Pt(111) as an example, we further show how the films enhance activity for hydrogen evolution through a bifunctional effect. The results suggest design principles for this class of electrocatalysts with simultaneously enhanced stability and activity for energy conversion.

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Acknowledgements

This work was supported through a Department of Energy Early Career award through the Office of Science, Office of Basic Energy Sciences, Chemical, Biological, and Geosciences Division under DE-SC0010379. Use of the Center for Nanoscale Materials and the Advanced Photon Source were supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract E-AC02-06CH11357. N.M.M. acknowledges support from the US Department of Energy Office of Science, Basic Energy Sciences, Division of Materials Sciences and Engineering. We acknowledge the computing resources provided on Blues and Fusion, a high-performance computing cluster operated by the Laboratory Computing Resource Center at Argonne National Laboratory, and the National Energy Research Scientific Computing Center (NERSC).

Author information

Affiliations

  1. Davidson School of Chemical Engineering, Purdue University, West Lafayette, Indiana 47907, USA

    • Zhenhua Zeng
    • , Joseph Kubal
    •  & Jeffrey Greeley
  2. Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, USA

    • Kee-Chul Chang
    •  & Nenad M. Markovic

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Contributions

Z.Z. and J.G. proposed the research direction, designed computations and guided the project. Z.Z. and J.K. performed the computations. K.-C.C. and N.M.M. designed, performed and analysed the experiments. Z.Z. and J.G. analysed the results and drafted the manuscript. All authors discussed the results and revised the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Jeffrey Greeley.

Supplementary information

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    Supplementary Information

    Supplementary Methods, Supplementary Discussion, Supplementary Tables 1–8, Supplementary Figures 1–31, Supplementary References.