E-resources
Peer reviewed
Open access
-
Zhang, Qiang; Asthagiri, Aravind
Catalysis today, 02/2019, Volume: 323, Issue: CJournal Article
Display omitted •Continuum solvation fails to predict oxygen reduction onset potential on Pt (111).•Main issue is an underestimation of OH solvation energy.•Adding 1 or 2 explicit water molecules does not correct the OH solvation energy. We present a comparison study between the implicit and explicit solvation approach for density functional theory (DFT) predictions of the oxygen reduction reaction (ORR) activity on Pt (111) and other metal surfaces under acidic conditions. DFT calculations with a self-consistent polarizable continuum model implement in VASPsol results in more accurate predictions of onset potentials for Pt(111) than vacuum DFT calculations due to the extra stabilization of the surface intermediates (OOH*, O*, OH*). Implicit solvation also preserves the scaling relationship among ORR intermediates and volcano-shape activity relationships that correlate ORR onset potential or activity to the free energy absorption of O* or OH*. Moreover, VASPsol predicts variation in the solvation energies across different surfaces, suggesting the use of universal solvation corrections may not be valid. However, VASPsol exhibits significant weaker OH* solvation energies (by ∼ 0.4 eV) on Pt (111) compared to literature values using an explicit water bilayer and therefore underestimates the onset potential on Pt (111). We attribute this lack of OH* solvation energies by VASPsol to its inability to address hydrogen bonds and the absence of intermediate stabilization of the bilayer structure. Strategies to mitigate this problem, including tuning VASPsol parameters and a hybrid approach incorporating one to two water molecules, are also examined but not found to alleviate the underestimation of the solvation of OH*.
![loading ... loading ...](themes/default/img/ajax-loading.gif)
Shelf entry
Permalink
- URL:
Impact factor
Access to the JCR database is permitted only to users from Slovenia. Your current IP address is not on the list of IP addresses with access permission, and authentication with the relevant AAI accout is required.
Year | Impact factor | Edition | Category | Classification | ||||
---|---|---|---|---|---|---|---|---|
JCR | SNIP | JCR | SNIP | JCR | SNIP | JCR | SNIP |
Select the library membership card:
If the library membership card is not in the list,
add a new one.
DRS, in which the journal is indexed
Database name | Field | Year |
---|
Links to authors' personal bibliographies | Links to information on researchers in the SICRIS system |
---|
Source: Personal bibliographies
and: SICRIS
The material is available in full text. If you wish to order the material anyway, click the Continue button.