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Title: Coverage-Dependent Adsorption of Phenol on Pt(111) from First Principles

Abstract

In this work, we quantify the coverage dependence of the adsorbate-adsorbate and metal-adsorbate interactions for phenol on Pt(111) using density functional theory. For the four most favorable adsorption sites, we find that the adsorption energy of phenol decreases linearly as a function of coverage. As such, the repulsive phenol-phenol lateral interactions are strongest near saturation when the inter-molecular distances are less than ~4.5 Å, manifesting in a decrease of the C-O dihedral bond angle of ~4°. The linear dependence of the adsorption energy on coverage allows for the construction of a mean-field model. We validate our mean-field model for phenol adsorption by comparing the theoretically predicted differential heat of adsorption to the experimental data, where a maximum deviation of 0.11 eV is found. This compares well to earlier reported results that used a similar mean-field approach for the adsorption of benzene on Pt(111), suggesting that lateral interactions between functionalized aromatics can be parameterized using a simpler approximation. Overall, this work demonstrates a simple method toward the improvement in current state-of-the-art hydrodeoxygenation modeling at surfaces by allowing for the incorporation of coverage effects in systems with large, aromatic compounds without resorting to overly complex models.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]
  1. Washington State Univ., Pullman, WA (United States)
  2. Washington State Univ., Pullman, WA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis
Publication Date:
Research Org.:
Washington State Univ., Pullman, WA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; Joint Center for Deployment and Research in Earth Abundant Materials (JCDREAM); National Science Foundation (NSF); Achievement Rewards for College Scientists Foundation
OSTI Identifier:
1656774
Grant/Contract Number:  
SC0014560; FG02-05ER15712; AC02-05CH11231; 1347973
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 124; Journal Issue: 1; Related Information: This work was also featured on the cover of the journal, which is available here:https://pubs.acs.org/pb-assets/images/_journalCovers/jpccck/jpccck_v124i001-2.jpg?0.8476531517166941; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 74 ATOMIC AND MOLECULAR PHYSICS; 97 MATHEMATICS AND COMPUTING; Hydrocarbons; Aromatic compounds; Energy; Adsorption; Molecules

Citation Formats

Chaudhary, Neeru, Hensley, Alyssa, Collinge, Greg, Wang, Yong, and McEwen, Jean-Sabin. Coverage-Dependent Adsorption of Phenol on Pt(111) from First Principles. United States: N. p., 2019. Web. https://doi.org/10.1021/acs.jpcc.9b07517.
Chaudhary, Neeru, Hensley, Alyssa, Collinge, Greg, Wang, Yong, & McEwen, Jean-Sabin. Coverage-Dependent Adsorption of Phenol on Pt(111) from First Principles. United States. https://doi.org/10.1021/acs.jpcc.9b07517
Chaudhary, Neeru, Hensley, Alyssa, Collinge, Greg, Wang, Yong, and McEwen, Jean-Sabin. Wed . "Coverage-Dependent Adsorption of Phenol on Pt(111) from First Principles". United States. https://doi.org/10.1021/acs.jpcc.9b07517. https://www.osti.gov/servlets/purl/1656774.
@article{osti_1656774,
title = {Coverage-Dependent Adsorption of Phenol on Pt(111) from First Principles},
author = {Chaudhary, Neeru and Hensley, Alyssa and Collinge, Greg and Wang, Yong and McEwen, Jean-Sabin},
abstractNote = {In this work, we quantify the coverage dependence of the adsorbate-adsorbate and metal-adsorbate interactions for phenol on Pt(111) using density functional theory. For the four most favorable adsorption sites, we find that the adsorption energy of phenol decreases linearly as a function of coverage. As such, the repulsive phenol-phenol lateral interactions are strongest near saturation when the inter-molecular distances are less than ~4.5 Å, manifesting in a decrease of the C-O dihedral bond angle of ~4°. The linear dependence of the adsorption energy on coverage allows for the construction of a mean-field model. We validate our mean-field model for phenol adsorption by comparing the theoretically predicted differential heat of adsorption to the experimental data, where a maximum deviation of 0.11 eV is found. This compares well to earlier reported results that used a similar mean-field approach for the adsorption of benzene on Pt(111), suggesting that lateral interactions between functionalized aromatics can be parameterized using a simpler approximation. Overall, this work demonstrates a simple method toward the improvement in current state-of-the-art hydrodeoxygenation modeling at surfaces by allowing for the incorporation of coverage effects in systems with large, aromatic compounds without resorting to overly complex models.},
doi = {10.1021/acs.jpcc.9b07517},
journal = {Journal of Physical Chemistry. C},
number = 1,
volume = 124,
place = {United States},
year = {2019},
month = {11}
}

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