TY - JOUR
T1 - Coverage-Dependent Adsorption of Phenol on Pt(111) from First Principles
AU - Chaudhary, Neeru
AU - Hensley, Alyssa
AU - Collinge, Greg
AU - Wang, Yong
AU - McEwen, Jean Sabin
N1 - Publisher Copyright:
Copyright © 2019 American Chemical Society.
PY - 2020/1/9
Y1 - 2020/1/9
N2 - 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 intermolecular 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.
AB - 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 intermolecular 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.
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U2 - 10.1021/acs.jpcc.9b07517
DO - 10.1021/acs.jpcc.9b07517
M3 - Article
AN - SCOPUS:85077204392
SN - 1932-7447
VL - 124
SP - 356
EP - 362
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 1
ER -