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SCALING RELATIONS

Mechanochemistry breaks with expectations

Nature Catalysis volume 1, pages 238–239 (2018)Cite this article

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Tensile strain of a solid surface can result in either strengthening or weakening of bonds with adsorbates. Adsorption energies of different adsorbate/site combinations may be shifted in different directions — a striking violation of the Brønsted–Evans–Polanyi relation.

Writing in Nature Catalysis, Khorshidi et al.5 derive the coupling between strain and adsorption energy from the local eigenstress fields around adsorbed molecules. They emphasize that the eigenstress can be of either sign — compressive or tensile — depending on the combination of adsorbed molecule and adsorption site. They show that the sign of the coupling between substrate strain and adsorption reflects the sign of the eigenstress. The consequences of this coupling break with established concepts in two respects: first, an imposed tensile strain of the surface can either strengthen or weaken the binding, whereas the classic d-band model1 of adsorption on strained surfaces invariably predicts stronger binding in response to tension. Second, as illustrated in Fig. 1, the coupling strength can differ strongly between different adsorbate/site combinations on the same surface. Khorshidi and colleagues emphasize that their more general account of chemomechanical coupling implies that a limitation imposed by the Brønsted–Evans–Polanyi relation can be circumvented: the relation implies that any change to the surface should invariably shift the adsorption energies of different intermediates in the same direction, whereas Khorshidi and co-workers demonstrate a more general behaviour with independent shifts that can take either sign. The rational application of mechanochemical coupling may therefore provide new opportunities in tailoring catalytic behaviour.

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Fig. 1: Relating atomic-scale mechanical interactions to experimental signatures in the macroscopic world.

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Authors and Affiliations

  1. Institut für Werkstoffphysik und Werkstofftechnologie, Technische Universität Hamburg, Hamburg, Germany

    Jörg Weissmüller

  2. Institut für Werkstoffforschung, Werkstoffmechanik, Helmholtz-Zentrum Geesthacht, Geesthacht, Germany

    Jörg Weissmüller

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  1. Jörg Weissmüller
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Correspondence to Jörg Weissmüller.

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Weissmüller, J. Mechanochemistry breaks with expectations. Nat Catal 1, 238–239 (2018). https://doi.org/10.1038/s41929-018-0061-1

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