Letter | Published:

Direct instrumental identification of catalytically active surface sites

Nature volume 549, pages 7477 (07 September 2017) | Download Citation

Abstract

The activity of heterogeneous catalysts—which are involved in some 80 per cent of processes in the chemical and energy industries—is determined by the electronic structure of specific surface sites that offer optimal binding of reaction intermediates. Directly identifying and monitoring these sites during a reaction should therefore provide insight that might aid the targeted development of heterogeneous catalysts and electrocatalysts (those that participate in electrochemical reactions) for practical applications. The invention of the scanning tunnelling microscope (STM)1,2 and the electrochemical STM3,4 promised to deliver such imaging capabilities, and both have indeed contributed greatly to our atomistic understanding of heterogeneous catalysis5,6,7,8. But although the STM has been used to probe and initiate surface reactions9,10, and has even enabled local measurements of reactivity in some systems11,12,13, it is not generally thought to be suited to the direct identification of catalytically active surface sites under reaction conditions. Here we demonstrate, however, that common STMs can readily map the catalytic activity of surfaces with high spatial resolution: we show that by monitoring relative changes in the tunnelling current noise, active sites can be distinguished in an almost quantitative fashion according to their ability to catalyse the hydrogen-evolution reaction or the oxygen-reduction reaction. These data allow us to evaluate directly the importance and relative contribution to overall catalyst activity of different defects and sites at the boundaries between two materials. With its ability to deliver such information and its ready applicability to different systems, we anticipate that our method will aid the rational design of heterogeneous catalysts.

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Acknowledgements

We thank the Deutsche Forschungsgemeinschaft (DFG; project BA 5795/3-1) and the cluster of excellence Nanosystems Initiative Munich (NIM) for financial support. O.S. acknowledges funding from Toyota Motor Europe.

Author information

Author notes

    • Jonas H. K. Pfisterer
    •  & Yunchang Liang

    These authors contributed equally to this work.

Affiliations

  1. Physics of Energy Conversion and Storage, Physik-Department, Technische Universität München, James-Franck-Straße 1, 85748 Garching, Germany

    • Jonas H. K. Pfisterer
    • , Yunchang Liang
    •  & Aliaksandr S. Bandarenka
  2. Institut für Informatik VI, Technische Universität München, Schleißheimerstraße 90a, 85748 Garching, Germany

    • Yunchang Liang
    •  & Oliver Schneider
  3. Nanosystems Initiative Munich (NIM), Schellingstraße 4, 80799 Munich, Germany

    • Yunchang Liang
    •  & Aliaksandr S. Bandarenka
  4. Catalysis Research Center TUM, Ernst-Otto-Fischer-Straße 1, 85748 Garching, Germany

    • Aliaksandr S. Bandarenka

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Contributions

J.H.K.P. and Y.L. conducted the experiments, performed the data analysis and contributed to manuscript preparation. A.S.B. developed the basic idea, wrote large parts of the manuscript and supervised J.H.K.P. and Y.L. in their experimental work. O.S. suggested the use of the palladium/gold system, contributed background knowledge, advised Y.L. in his experimental work and contributed to the manuscript-drafting process. All the authors participated in discussing the results and writing the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Aliaksandr S. Bandarenka.

Reviewer Information Nature thanks S. Boettcher, P. Davies and J. Kunze-Liebhäuser for their contribution to the peer review of this work.

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https://doi.org/10.1038/nature23661

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