Affordable Estimation of Solvation Contributions to the Adsorption Energies of Oxygenates on Metal Nanoparticles
Abstract
Electrocatalysts are mainly characterized by their intrinsic adsorption properties. However, the observed electrocatalytic activity ultimately results from the interplay between such properties and various additional interactions within the electrified solid–liquid interface. One of such phenomena is solvation, which can substantially affect the stability of adsorbates. The incorporation of solvation in computational electrocatalysis models can be fully implicit (inaccurate for H-bonded adsorbates), fully explicit (challenging computation of free energies), or embedded. Here, we show that without any need for explicit or implicit media, a microsolvation approach with just three water molecules captures the contribution of co-adsorbed water to the adsorption energies of *OH and *OOH (two important adsorbates for oxygen reduction) on platinum nanoparticles of various sizes. The approach enables an accurate yet inexpensive explicit modeling of solvent–adsorbate interactions in nanoparticles and the calculation of solvation corrections, estimated as -0.59 ± 0.14 and -0.47 ± 0.13 eV for *OH and *OOH adsorption on Pt, respectively.
- Authors:
-
[1];
[1];
[2];
[3]
- Univ. de Barcelona, Barcelona (Spain). Dept. de Ciència de Materials i Química Fisica, Inst. de Química Teòrica i Computacional (IQTCUB)
- Univ. Lyon, Lyon (France). Lab. de Chimie
- Univ. of California, Los Angeles, CA (United States). Dept. of Chemistry and Biochemistry, and Dept. of Chemical and Biomolecular Engineering
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Synthetic Control Across Length-scales for Advancing Rechargeables (SCALAR); Univ. of California, Los Angeles, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1566532
- Grant/Contract Number:
- SC0019381
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 123; Journal Issue: 9; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; electrocatalysis, electrical energy storage, defects, charge transport, mesoscale science, materials and chemistry by design, mesostructured materials, synthesis (novel materials), synthesis (scalable processing)
Citation Formats
Calle-Vallejo, Federico, F. de Morais, Rodrigo, Illas, Francesc, Loffreda, David, and Sautet, Philippe. Affordable Estimation of Solvation Contributions to the Adsorption Energies of Oxygenates on Metal Nanoparticles. United States: N. p., 2019.
Web. doi:10.1021/acs.jpcc.9b01211.
Calle-Vallejo, Federico, F. de Morais, Rodrigo, Illas, Francesc, Loffreda, David, & Sautet, Philippe. Affordable Estimation of Solvation Contributions to the Adsorption Energies of Oxygenates on Metal Nanoparticles. United States. https://doi.org/10.1021/acs.jpcc.9b01211
Calle-Vallejo, Federico, F. de Morais, Rodrigo, Illas, Francesc, Loffreda, David, and Sautet, Philippe. Fri .
"Affordable Estimation of Solvation Contributions to the Adsorption Energies of Oxygenates on Metal Nanoparticles". United States. https://doi.org/10.1021/acs.jpcc.9b01211. https://www.osti.gov/servlets/purl/1566532.
@article{osti_1566532,
title = {Affordable Estimation of Solvation Contributions to the Adsorption Energies of Oxygenates on Metal Nanoparticles},
author = {Calle-Vallejo, Federico and F. de Morais, Rodrigo and Illas, Francesc and Loffreda, David and Sautet, Philippe},
abstractNote = {Electrocatalysts are mainly characterized by their intrinsic adsorption properties. However, the observed electrocatalytic activity ultimately results from the interplay between such properties and various additional interactions within the electrified solid–liquid interface. One of such phenomena is solvation, which can substantially affect the stability of adsorbates. The incorporation of solvation in computational electrocatalysis models can be fully implicit (inaccurate for H-bonded adsorbates), fully explicit (challenging computation of free energies), or embedded. Here, we show that without any need for explicit or implicit media, a microsolvation approach with just three water molecules captures the contribution of co-adsorbed water to the adsorption energies of *OH and *OOH (two important adsorbates for oxygen reduction) on platinum nanoparticles of various sizes. The approach enables an accurate yet inexpensive explicit modeling of solvent–adsorbate interactions in nanoparticles and the calculation of solvation corrections, estimated as -0.59 ± 0.14 and -0.47 ± 0.13 eV for *OH and *OOH adsorption on Pt, respectively.},
doi = {10.1021/acs.jpcc.9b01211},
journal = {Journal of Physical Chemistry. C},
number = 9,
volume = 123,
place = {United States},
year = {Fri Feb 08 00:00:00 EST 2019},
month = {Fri Feb 08 00:00:00 EST 2019}
}
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