Coverage-Dependent Adsorption of Phenol on Pt(111) from First Principles
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.
- Research Organization:
- Washington State Univ., Pullman, WA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
- Sponsoring Organization:
- 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
- Grant/Contract Number:
- SC0014560; FG02-05ER15712; AC02-05CH11231; 1347973
- OSTI ID:
- 1656774
- Journal Information:
- Journal of Physical Chemistry. C, Vol. 124, 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; ISSN 1932-7447
- Publisher:
- American Chemical SocietyCopyright Statement
- Country of Publication:
- United States
- Language:
- English
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