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

  • 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]
  • 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
  • E. Charles H. Sykes
    E. Charles H. Sykes
    Department of Chemistry, Tufts University, 62 Talbot Avenue, Medford, Massachusetts 02155, United States
  • Michail Stamatakis
    Michail Stamatakis
    Department of Chemical Engineering, University College London, Roberts Building, Torrington Place, London WC1E 7JE, U.K.
  • , and 
  • 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]
Cite this: J. Phys. Chem. Lett. 2021, 12, 41, 10060–10067
Publication Date (Web):October 11, 2021
https://doi.org/10.1021/acs.jpclett.1c02497
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.

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    Cited By

    This article is cited by 14 publications.

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    2. Yixiao Wang, Mengdan Wei, Qingdan Ding, Huimin Li, Wei Ma. Identification of Intersite Distance Effects in Au-Ag Single-Atom Alloy Catalysts Using Single Nanoparticle Collision Electrochemistry. Nano Letters 2024, 24 (16) , 4733-4740. https://doi.org/10.1021/acs.nanolett.3c04006
    3. Zhenghui Tan, Jun Chen, Sen Lin. Theoretical Insights into H2 Activation and Hydrogen Spillover on Near-Surface Alloys with Embedded Single Pt Atoms. ACS Catalysis 2024, 14 (4) , 2194-2201. https://doi.org/10.1021/acscatal.3c05660
    4. Raz L. Benson, Sai Sharath Yadavalli, Michail Stamatakis. Speeding up the Detection of Adsorbate Lateral Interactions in Graph-Theoretical Kinetic Monte Carlo Simulations. The Journal of Physical Chemistry A 2023, 127 (48) , 10307-10319. https://doi.org/10.1021/acs.jpca.3c05581
    5. Beomil Kim, Ying Chuan Tan, Yeonkyeong Ryu, Kyuseon Jang, Hafiz Ghulam Abbas, Taehyeok Kang, Hyeonuk Choi, Kug-Seung Lee, Sojung Park, Wooyul Kim, Pyuck-Pa Choi, Stefan Ringe, Jihun Oh. Trace-Level Cobalt Dopants Enhance CO2 Electroreduction and Ethylene Formation on Copper. ACS Energy Letters 2023, 8 (8) , 3356-3364. https://doi.org/10.1021/acsenergylett.3c00418
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    9. Romain Réocreux, E. Charles H. Sykes, Angelos Michaelides, Michail Stamatakis. Stick or Spill? Scaling Relationships for the Binding Energies of Adsorbates on Single-Atom Alloy Catalysts. The Journal of Physical Chemistry Letters 2022, 13 (31) , 7314-7319. https://doi.org/10.1021/acs.jpclett.2c01519
    10. Ziyi Chen, Peng Zhang. Electronic Structure of Single-Atom Alloys and Its Impact on The Catalytic Activities. ACS Omega 2022, 7 (2) , 1585-1594. https://doi.org/10.1021/acsomega.1c06067
    11. Ricardo Ruvalcaba, Jonathan Guerrero-Sanchez, Noboru Takeuchi, Francisco Zaera. Crotonaldehyde Adsorption on Cu-Pt Surface Alloys: A Quantum Mechanics Study. Chemistry 2023, 5 (1) , 463-478. https://doi.org/10.3390/chemistry5010034
    12. Tongxin Han, Yuanyuan Li, Yueqiang Cao, Ilkeun Lee, Xinggui Zhou, Anatoly I. Frenkel, Francisco Zaera. In situ identification of surface sites in Cu–Pt bimetallic catalysts: Gas-induced metal segregation. The Journal of Chemical Physics 2022, 157 (23) , 234706. https://doi.org/10.1063/5.0130431
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    14. M. Pineda, M. Stamatakis. Kinetic Monte Carlo simulations for heterogeneous catalysis: Fundamentals, current status, and challenges. The Journal of Chemical Physics 2022, 156 (12) , 120902. https://doi.org/10.1063/5.0083251

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