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Engineering the Surface Architecture of Highly Dilute Alloys: An ab Initio Monte Carlo Approach

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    Research Article

    Engineering the Surface Architecture of Highly Dilute Alloys: An ab Initio Monte Carlo Approach
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    ACS Catalysis

    Cite this: ACS Catal. 2020, 10, 2, 1224–1236
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    https://doi.org/10.1021/acscatal.9b04029
    Published November 11, 2019
    Copyright © 2019 American Chemical Society
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    Abstract

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    Highly dilute alloys of platinum group metals (PGMs: Pt, Rh, Ir, Pd, and Ni) with coinage metals (Cu, Au, and Ag) serve as highly selective and coke-resistant catalysts in a number of applications. The catalytic behavior of these materials is governed by the size and shape of the surface “ensembles” of PGM atoms. Therefore, establishing a means of control over the topological architecture of highly dilute alloy surfaces is crucial to optimizing their catalytic performance. In the present work, we use on-lattice Monte Carlo simulations that are parameterized by density functional theory-derived energetics to investigate the surface aggregation of PGM atoms under vacuum conditions and in the presence of CO. We study several highly dilute alloy surfaces at various PGM loadings, including Pd/Au(111), Pd/Ag(111), Pt/Cu(111), Rh/Cu(111), Ir/Ag(111), and Ni/Cu(111). Under vacuum conditions, we observe a thermodynamic preference for dispersion of PGM as single atoms in the surface of the coinage metal host, on all examined alloy surfaces except Ir/Ag(111), where Ir atom aggregation and island formation is preferred. By evaluating the alloy surface structure in the presence of CO, we determine that the size and shape of PGM ensembles can be manipulated by tuning the partial pressure of CO (PCO) on the Pd/Au(111), Pd/Ag(111), Ir/Ag(111), and Ni/Cu(111) surfaces. In contrast, we determine that Pt/Cu(111) and Rh/Cu(111) highly dilute alloys are unresponsive to changes in PCO with Rh and Pt dispersing as isolated single atoms within the host matrix, irrespective of gaseous composition. Our findings suggest that it may be possible to fine-tune the surface architecture of highly dilute binary alloys for optimized catalytic performance.

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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/acscatal.9b04029.

    • Finite lattice size testing, figures included in the cluster expansions of this work, DFT geometries used for the fitting of the cluster expansions, Cook’s distances, average properties in Monte Carlo simulations, calculation of pre-exponential ratios for CO diffusion, vibrational frequencies of CO adsorbed on different sites and maximum CO pressures used in the simulations, calculation of partition functions for CO adsorption/desorption, representative images of the DFT slab and Monte Carlo snapshots, electronic aspects of surface aggregation, calculating the formation energy of a DFT geometry, Monte Carlo simulation bias testing (PDF)

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    ACS Catalysis

    Cite this: ACS Catal. 2020, 10, 2, 1224–1236
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acscatal.9b04029
    Published November 11, 2019
    Copyright © 2019 American Chemical Society
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