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Introducing structural sensitivity into adsorption–energy scaling relations by means of coordination numbers

Nature Chemistry volume 7, pages 403–410 (2015)Cite this article

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Abstract

The search for improved heterogeneous catalysts is an important but difficult task. Scaling relations between the adsorption energies of reaction intermediates greatly facilitate the computational design of catalysts. However, this methodology does not currently incorporate structure sensitivity and hence cannot describe adequately the overall activity of realistic catalyst particles and extended surfaces with several facets, edges and apices. Here, we generalize scaling relations by examining twelve different low-index, stepped and kinked surfaces of nine transition metals. This allows us to quantify the effect of the adsorption-site geometry on these relations, ensures a full prediction of their parameters, and helps in identifying intrinsic thermodynamic restrictions to the performance of catalysts. The resulting fully predictable, structure-sensitive scaling relations are a step towards the long-sought rational design of multifaceted catalytic particles. Such a design can now target not only the chemical nature of active materials but also the actual geometry of their active sites.

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Figure 1: Schematics of the twelve surface sites included in this study.
Figure 2: Scaling relations between oxygen and oxygenates generalized for twelve different types of surface site on nine transition metals.
Figure 3: Structure–energy relations for atomic oxygen and oxygenates.
Figure 4: Scaling relations between the adsorption energies of oxygenates: *OOH versus *OH (diamonds) and *OCH3 versus *OH (triangles).
Figure 5: Comparison between the energies of adsorption (ΔEDFT) of oxygenates calculated with DFT and energies estimated using universal scaling relations (ΔEpredicted).

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Acknowledgements

The authors acknowledge funding from the EU, grant n°303419 (PUMA MIND). The authors thank NCF, IDRIS, CINES and PSMN for CPU time and assistance. The authors thank A. Bandarenka and J.M. García-Lastra for critical reading of this article.

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Authors and Affiliations

  1. Université de Lyon, CNRS, Laboratoire de Chimie, ENS Lyon, 46 Allée d'Italie, Lyon Cedex 07, 69364, France

    Federico Calle-Vallejo, David Loffreda & Philippe Sautet

  2. Leiden Institute of Chemistry, Leiden University, Leiden, 2300, RA, The Netherlands

    Marc T. M. Koper

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  1. Federico Calle-Vallejo
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F.C-V. made all of the DFT calculations. All authors participated in the discussion of the results and the writing of the manuscript.

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Correspondence to Federico Calle-Vallejo or Philippe Sautet.

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Calle-Vallejo, F., Loffreda, D., Koper, M. et al. Introducing structural sensitivity into adsorption–energy scaling relations by means of coordination numbers. Nature Chem 7, 403–410 (2015). https://doi.org/10.1038/nchem.2226

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