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Title: Influence of Van der Waals Interactions on the Solvation Energies of Adsorbates at Pt-Based Electrocatalysts

Abstract

Solvation can significantly modify the adsorption energy of species at surfaces, thereby influencing the performance of electrocatalysts and liquid-phase catalysts. Thus, it is important to understand adsorbate solvation at the nanoscale. Here we evaluate the effect of van der Waals (vdW) interactions described by different approaches on the solvation energy of *OH adsorbed on near-surface alloys (NSAs) of Pt. Our results show that the studied functionals can be divided into two groups, each with rather similar average *OH solvation energies: (1) PBE and PW91; and (2) vdW functionals, RPBE, PBE-D3 and RPBE-D3. On average, *OH solvation energies are less negative by ~0.14 eV in group (2) compared to (1), and the values for a given alloy can be extrapolated from one functional to another within the same group. Depending on the desired level of accuracy, these concrete observations and our tabulated values can be used to rapidly incorporate solvation into models for electrocatalysis and liquid-phase catalysis.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [3]
  1. Leiden Univ. (Netherlands)
  2. Univ. EAFIT, Medellín (Colombia)
  3. Univ. de Barcelona (Spain)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Sponsoring Org.:
USDOE Office of Science (SC); Ramón y Cajal; Units of Excellence María de Maeztu; Netherlands Organization for Scientific Research (NWO); European Union (EU)
OSTI Identifier:
1623518
Grant/Contract Number:  
SC0012704; RYC-2015-18996; MDM-2017-0767
Resource Type:
Accepted Manuscript
Journal Name:
ChemPhysChem
Additional Journal Information:
Journal Volume: 20; Journal Issue: 22; Journal ID: ISSN 1439-4235
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; chemistry; physics; adsorbate solvation; density functional theory; near-surface alloys; oxygen reduction reaction; platinum

Citation Formats

Granda‐Marulanda, Laura P., Builes, Santiago, Koper, Marc T. M., and Calle‐Vallejo, Federico. Influence of Van der Waals Interactions on the Solvation Energies of Adsorbates at Pt-Based Electrocatalysts. United States: N. p., 2019. Web. https://doi.org/10.1002/cphc.201900512.
Granda‐Marulanda, Laura P., Builes, Santiago, Koper, Marc T. M., & Calle‐Vallejo, Federico. Influence of Van der Waals Interactions on the Solvation Energies of Adsorbates at Pt-Based Electrocatalysts. United States. https://doi.org/10.1002/cphc.201900512
Granda‐Marulanda, Laura P., Builes, Santiago, Koper, Marc T. M., and Calle‐Vallejo, Federico. Fri . "Influence of Van der Waals Interactions on the Solvation Energies of Adsorbates at Pt-Based Electrocatalysts". United States. https://doi.org/10.1002/cphc.201900512. https://www.osti.gov/servlets/purl/1623518.
@article{osti_1623518,
title = {Influence of Van der Waals Interactions on the Solvation Energies of Adsorbates at Pt-Based Electrocatalysts},
author = {Granda‐Marulanda, Laura P. and Builes, Santiago and Koper, Marc T. M. and Calle‐Vallejo, Federico},
abstractNote = {Solvation can significantly modify the adsorption energy of species at surfaces, thereby influencing the performance of electrocatalysts and liquid-phase catalysts. Thus, it is important to understand adsorbate solvation at the nanoscale. Here we evaluate the effect of van der Waals (vdW) interactions described by different approaches on the solvation energy of *OH adsorbed on near-surface alloys (NSAs) of Pt. Our results show that the studied functionals can be divided into two groups, each with rather similar average *OH solvation energies: (1) PBE and PW91; and (2) vdW functionals, RPBE, PBE-D3 and RPBE-D3. On average, *OH solvation energies are less negative by ~0.14 eV in group (2) compared to (1), and the values for a given alloy can be extrapolated from one functional to another within the same group. Depending on the desired level of accuracy, these concrete observations and our tabulated values can be used to rapidly incorporate solvation into models for electrocatalysis and liquid-phase catalysis.},
doi = {10.1002/cphc.201900512},
journal = {ChemPhysChem},
number = 22,
volume = 20,
place = {United States},
year = {2019},
month = {7}
}

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Cited by: 2 works
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Figures / Tables:

Figure 1 Figure 1: Schematics of Equations 1 and 2 for the free energies of formation of *OH on Pt NSAs. (a) 1/3 ML *OH coadsorbed with 1/3 ML *H2O (right side) using as a reference a water bilayer (left side) with one water molecule parallel to the surface plane and themore » other one with a hydrogen atom pointing towards the surface. (b) 1/3 ML *OH in vacuum (right side) using liquid water as a reference (left side). In both cases the slabs are 2 x 2 repetitions of a (111) $\sqrt{3}$ x $\sqrt{3}$ R30° supercell defined by the yellow dashed lines. Each layer in the slab contains 3 metal atoms. Pt: gray, subsurface metal: green, O in H2O: red, O in OH: purple, H: white. Top and side views of the water adlayer are shown in Figure S3.« less

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      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.