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Distribution Tendencies of Noble Metals on Fe(100) Using Lattice Gas Cluster Expansions
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    Distribution Tendencies of Noble Metals on Fe(100) Using Lattice Gas Cluster Expansions
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    • Isaac Onyango
      Isaac Onyango
      The Gene and Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, Washington 99163, United States
    • Greg Collinge
      Greg Collinge
      The Gene and Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, Washington 99163, United States
    • Yong Wang
      Yong Wang
      The Gene and Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, Washington 99163, United States
      Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
      More by Yong Wang
    • Jean-Sabin McEwen*
      Jean-Sabin McEwen
      The Gene and Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, Washington 99163, United States
      Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
      Department of Physics and Astronomy, Washington State University, Pullman, Washington 99164, United States
      Department of Chemistry, Washington State University, Pullman, Washington 99164, United States
      Department of Biological Systems Engineering, Washington State University, Pullman, Washington 99164, United States
      *Email: [email protected]
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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2024, 128, 23, 9504–9512
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    https://doi.org/10.1021/acs.jpcc.4c01402
    Published May 30, 2024
    Copyright © 2024 The Authors. Published by American Chemical Society

    Abstract

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    Fe-based catalysts are highly selective for the hydrodeoxygenation of biomass-derived oxygenates but are prone to oxidative deactivation. Promotion with a noble metal has been shown to improve oxidative resistance. The chemical properties of such bimetallic systems depend critically on the surface geometry and spatial configuration of surface atoms in addition to their coverage (i.e., noble metal loading), so these aspects must be taken into account in order to develop reliable models for such complex systems. This requires sampling a vast configurational space, which is rather impractical using density functional theory (DFT) calculations alone. Moreover, “DFT-based” models are limited to length scales that are often too small for experimental relevance. Here, we circumvent this challenge by constructing DFT-parametrized lattice gas cluster expansions (LG CEs), which can describe these types of systems at significantly larger length scales. Here, we apply this strategy to Fe(100) promoted with four technologically relevant precious metals: Pd, Pt, Rh, and Ru. The resultant LG CEs have remarkable predictive accuracy, with predictive errors below 10 meV/site over a coverage range of 0 to 2 monolayers. The ground state configurations for each noble metal were identified, and the analysis of the cluster energies reveals a significant disparity in their dispersion tendency.

    Copyright © 2024 The Authors. Published by American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpcc.4c01402.

    • Parity plots (Figure S1); convex hulls (Figure S2); LMO CV (Figure S3); 1-body clusters (Figure S4); 3-body, 4-body, and 5-body clusters (Figures S5–S8); Pd/Fe(100) convex hulls (Figure S10); Pt/Fe(100) convex hulls (Figure S11); Rh/Fe(100) convex hulls (Figure S12); and Ru/Fe(100) convex hulls (Figure S13) (PDF)

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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2024, 128, 23, 9504–9512
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpcc.4c01402
    Published May 30, 2024
    Copyright © 2024 The Authors. Published by American Chemical Society

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