Quantifying the impact of relativity and of dispersion interactions on the activation of molecular oxygen promoted by noble metal nanoparticles

Handle URI:
http://hdl.handle.net/10754/563611
Title:
Quantifying the impact of relativity and of dispersion interactions on the activation of molecular oxygen promoted by noble metal nanoparticles
Authors:
Kanoun, Mohammed; Cavallo, Luigi ( 0000-0002-1398-338X )
Abstract:
We compared the mechanism of O2 dissociation catalyzed by Cu38, Ag38, and Au38 nanoparticles. Overall, our results indicate that O2 dissociation is extremely easy on Cu38, with an almost negligible barrier for the O-O breaking step. It presents an energy barrier close to 20 kcal/mol on Ag38, which decreases to slightly more than 10 kcal/mol on Au38. This behavior is analyzed to quantify the impact of relativity and of dispersion interactions through a comparison of nonrelativistic, scalar-relativistic, and dispersioncorrected DFT methods. Nonrelativistic calculations show a clear trend down the triad, with larger in size nanoparticle (NP), weaker O2 adsorption energy, and higher O2 dissociation barrier, which is so high for Au38 to be in sharp contrast with the mild conditions used experimentally. Inclusion of relativity has no impact on the O2 adsorption energy, but it reduces the energy barrier for O2 dissociation on Au38 from 30.1 to 11.4 kcal/mol, making it even lower than that on Ag38 and consistent with the mild conditions used experimentally. Dispersion interactions have a remarkable role in improving the adsorption ability of O2 on the heavier Ag38 and especially Au38 NPs, contributing roughly 50% of the total adsorption energy, while they have much less impact on O2 adsorption on Cu38.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program
Publisher:
American Chemical Society (ACS)
Journal:
The Journal of Physical Chemistry C
Issue Date:
26-Jun-2014
DOI:
10.1021/jp503853f
Type:
Article
ISSN:
19327447
Sponsors:
Research reported in this publication was supported by the King Abdullah University of Science and Technology (KAUST).
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorKanoun, Mohammeden
dc.contributor.authorCavallo, Luigien
dc.date.accessioned2015-08-03T11:55:38Zen
dc.date.available2015-08-03T11:55:38Zen
dc.date.issued2014-06-26en
dc.identifier.issn19327447en
dc.identifier.doi10.1021/jp503853fen
dc.identifier.urihttp://hdl.handle.net/10754/563611en
dc.description.abstractWe compared the mechanism of O2 dissociation catalyzed by Cu38, Ag38, and Au38 nanoparticles. Overall, our results indicate that O2 dissociation is extremely easy on Cu38, with an almost negligible barrier for the O-O breaking step. It presents an energy barrier close to 20 kcal/mol on Ag38, which decreases to slightly more than 10 kcal/mol on Au38. This behavior is analyzed to quantify the impact of relativity and of dispersion interactions through a comparison of nonrelativistic, scalar-relativistic, and dispersioncorrected DFT methods. Nonrelativistic calculations show a clear trend down the triad, with larger in size nanoparticle (NP), weaker O2 adsorption energy, and higher O2 dissociation barrier, which is so high for Au38 to be in sharp contrast with the mild conditions used experimentally. Inclusion of relativity has no impact on the O2 adsorption energy, but it reduces the energy barrier for O2 dissociation on Au38 from 30.1 to 11.4 kcal/mol, making it even lower than that on Ag38 and consistent with the mild conditions used experimentally. Dispersion interactions have a remarkable role in improving the adsorption ability of O2 on the heavier Ag38 and especially Au38 NPs, contributing roughly 50% of the total adsorption energy, while they have much less impact on O2 adsorption on Cu38.en
dc.description.sponsorshipResearch reported in this publication was supported by the King Abdullah University of Science and Technology (KAUST).en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleQuantifying the impact of relativity and of dispersion interactions on the activation of molecular oxygen promoted by noble metal nanoparticlesen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.identifier.journalThe Journal of Physical Chemistry Cen
kaust.authorKanoun, Mohammeden
kaust.authorCavallo, Luigien
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