dc.contributor.author
Töpfer, Kai
dc.contributor.author
Tremblay, Jean Christophe
dc.date.accessioned
2018-06-08T03:28:25Z
dc.date.available
2016-08-02T12:05:59.699Z
dc.identifier.uri
https://refubium.fu-berlin.de/handle/fub188/15261
dc.identifier.uri
http://dx.doi.org/10.17169/refubium-19449
dc.description.abstract
In this contribution, we study using first principles the co-adsorption and
catalytic behaviors of CO and O2 on a single gold atom deposited at defective
magnesium oxide surfaces. Using cluster models and point charge embedding
within a density functional theory framework, we simulate the CO oxidation
reaction for Au1 on differently charged oxygen vacancies of MgO(001) to
rationalize its experimentally observed lack of catalytic activity. Our
results show that: (1) co-adsorption is weakly supported at F0 and F2+ defects
but not at F1+ sites, (2) electron redistribution from the F0 vacancy via the
Au1 cluster to the adsorbed molecular oxygen weakens the O2 bond, as required
for a sustainable catalytic cycle, (3) a metastable carbonate intermediate can
form on defects of the F0 type, (4) only a small activation barrier exists for
the highly favorable dissociation of CO2 from F0, and (5) the moderate
adsorption energy of the gold atom on the F0 defect cannot prevent insertion
of molecular oxygen inside the defect. Due to the lack of protection of the
color centers, the surface becomes invariably repaired by the surrounding
oxygen and the catalytic cycle is irreversibly broken in the first oxidation
step.
de
dc.format.extent
8 Seiten
dc.rights.uri
http://creativecommons.org/licenses/by-nc/3.0/
dc.subject.ddc
500 Naturwissenschaften und Mathematik::540 Chemie
dc.title
How surface reparation prevents catalytic oxidation of carbon monoxide on
atomic gold at defective magnesium oxide surfaces
dc.type
Wissenschaftlicher Artikel
dcterms.bibliographicCitation
Phys. Chem. Chem. Phys., 2016,18, 18590-18597
dcterms.bibliographicCitation.doi
10.1039/c6cp02339h
dcterms.bibliographicCitation.url
https://doi.org/10.1039/C6CP02339H
refubium.affiliation
Biologie, Chemie, Pharmazie
de
refubium.funding
OpenAccess Publikation in Allianzlizenz
refubium.funding.id
Au-028844
refubium.mycore.fudocsId
FUDOCS_document_000000025046
refubium.resourceType.isindependentpub
no
refubium.mycore.derivateId
FUDOCS_derivate_000000006794
dcterms.accessRights.openaire
open access