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Title: Effects of ensembles, ligand, and strain on adsorbate binding to alloy surfaces

Abstract

Alloying elements with strong and weak adsorption properties can produce a catalyst with optimally tuned adsorbate binding. A full understanding of this alloying effect, however, is not well-established. Here, we use density functional theory to study the ensemble, ligand, and strain effects of close-packed surfaces alloyed by transition metals with a combination of strong and weak adsorption of H and O. Specifically, we consider PdAu, RhAu, and PtAu bimetallics as ordered and randomly alloyed (111) surfaces, as well as randomly alloyed 140-atom clusters. In these alloys, Au is the weak-binding component and Pd, Rh, and Pt are characteristic strong-binding metals. In order to separate the different effects of alloying on binding, we calculate the tunability of H- and O-binding energies as a function of lattice constant (strain effect), number of alloy-substituted sublayers (ligand effect), and randomly alloyed geometries (ensemble effect). We find that on these alloyed surfaces, the ensemble effect more significantly tunes the adsorbate binding as compared to the ligand and strain effects, with the binding energies predominantly determined by the local adsorption environment provided by the specific triatomic ensemble on the (111) surface. However, we also find that tuning of adsorbate binding from the ligand and strain effectsmore » cannot be neglected in a quantitative description. Extending our studies to other bimetallics (PdAg, RhAg, PtAg, PdCu, RhCu, and PtCu), we find similar conclusions that the tunability of adsorbate binding on random alloys is predominately described by the ensemble effect.« less

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Texas, Austin, TX (United States). Dept. of Chemistry and the Institute for Computational Engineering and Sciences
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of Texas, Austin, TX (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1543889
Grant/Contract Number:  
SC0010576
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 149; Journal Issue: 17; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
Chemistry; Physics

Citation Formats

Li, Hao, Shin, Kihyun, and Henkelman, Graeme. Effects of ensembles, ligand, and strain on adsorbate binding to alloy surfaces. United States: N. p., 2018. Web. doi:10.1063/1.5053894.
Li, Hao, Shin, Kihyun, & Henkelman, Graeme. Effects of ensembles, ligand, and strain on adsorbate binding to alloy surfaces. United States. doi:10.1063/1.5053894.
Li, Hao, Shin, Kihyun, and Henkelman, Graeme. Fri . "Effects of ensembles, ligand, and strain on adsorbate binding to alloy surfaces". United States. doi:10.1063/1.5053894. https://www.osti.gov/servlets/purl/1543889.
@article{osti_1543889,
title = {Effects of ensembles, ligand, and strain on adsorbate binding to alloy surfaces},
author = {Li, Hao and Shin, Kihyun and Henkelman, Graeme},
abstractNote = {Alloying elements with strong and weak adsorption properties can produce a catalyst with optimally tuned adsorbate binding. A full understanding of this alloying effect, however, is not well-established. Here, we use density functional theory to study the ensemble, ligand, and strain effects of close-packed surfaces alloyed by transition metals with a combination of strong and weak adsorption of H and O. Specifically, we consider PdAu, RhAu, and PtAu bimetallics as ordered and randomly alloyed (111) surfaces, as well as randomly alloyed 140-atom clusters. In these alloys, Au is the weak-binding component and Pd, Rh, and Pt are characteristic strong-binding metals. In order to separate the different effects of alloying on binding, we calculate the tunability of H- and O-binding energies as a function of lattice constant (strain effect), number of alloy-substituted sublayers (ligand effect), and randomly alloyed geometries (ensemble effect). We find that on these alloyed surfaces, the ensemble effect more significantly tunes the adsorbate binding as compared to the ligand and strain effects, with the binding energies predominantly determined by the local adsorption environment provided by the specific triatomic ensemble on the (111) surface. However, we also find that tuning of adsorbate binding from the ligand and strain effects cannot be neglected in a quantitative description. Extending our studies to other bimetallics (PdAg, RhAg, PtAg, PdCu, RhCu, and PtCu), we find similar conclusions that the tunability of adsorbate binding on random alloys is predominately described by the ensemble effect.},
doi = {10.1063/1.5053894},
journal = {Journal of Chemical Physics},
number = 17,
volume = 149,
place = {United States},
year = {2018},
month = {11}
}

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