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Periodic Trends in Adsorption Energies around Single-Atom Alloy Active Sites

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    Physical Insights into Chemistry, Catalysis, and Interfaces

    Periodic Trends in Adsorption Energies around Single-Atom Alloy Active Sites
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    • Julia Schumann*
      Julia Schumann
      Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT, U.K.
      Department of Chemical Engineering, University College London, Roberts Building, Torrington Place, London WC1E 7JE, U.K.
      Yusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, U.K.
      *Email: [email protected]
      More by Julia Schumann
      Orcidhttps://orcid.org/0000-0002-4041-0165
    • Yutian Bao
      Yutian Bao
      Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT, U.K.
      More by Yutian Bao
    • Ryan T. Hannagan
      Ryan T. Hannagan
      Department of Chemistry, Tufts University, 62 Talbot Avenue, Medford, Massachusetts 02155, United States
      More by Ryan T. Hannagan
    • E. Charles H. Sykes
      E. Charles H. Sykes
      Department of Chemistry, Tufts University, 62 Talbot Avenue, Medford, Massachusetts 02155, United States
      More by E. Charles H. Sykes
      Orcidhttps://orcid.org/0000-0002-0224-2084
    • Michail Stamatakis
      Michail Stamatakis
      Department of Chemical Engineering, University College London, Roberts Building, Torrington Place, London WC1E 7JE, U.K.
      More by Michail Stamatakis
      Orcidhttps://orcid.org/0000-0001-8338-8706
    • Angelos Michaelides*
      Angelos Michaelides
      Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT, U.K.
      Yusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, U.K.
      *Email: [email protected]
      More by Angelos Michaelides
      Orcidhttps://orcid.org/0000-0002-9169-169X
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    The Journal of Physical Chemistry Letters

    Cite this: J. Phys. Chem. Lett. 2021, 12, 41, 10060–10067
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpclett.1c02497
    Published October 11, 2021
    Copyright © 2021 American Chemical Society
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    Abstract

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    Single-atom alloys (SAAs) make up a special class of alloy surface catalysts that offer well-defined, isolated active sites in a more inert metal host. The dopant sites are generally assumed to have little or no influence on the properties of the host metal, and transport of chemical reactants and products to and from the dopant sites is generally assumed to be facile. Here, by performing density functional theory calculations and surface science experiments, we identify a new physical effect on SAA surfaces, whereby adsorption is destabilized by ≤300 meV on host sites within the perimeter of the reactive dopant site. We identify periodic trends for this behavior and demonstrate a zone of exclusion around the reactive sites for a range of adsorbates and combinations of host and dopant metals. Experiments confirm an increased barrier for diffusion of CO toward the dopant on a RhCu SAA. This effect offers new possibilities for understanding and designing active sites with tunable energetic landscapes surrounding them.

    Copyright © 2021 American Chemical Society

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    The Journal of Physical Chemistry Letters

    Cite this: J. Phys. Chem. Lett. 2021, 12, 41, 10060–10067
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpclett.1c02497
    Published October 11, 2021
    Copyright © 2021 American Chemical Society
    Request reuse permissions

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