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dc.contributor.author
Hahn, Konstanze R.
dc.contributor.author
Baiker, Alfons
dc.date.accessioned
2022-12-30T12:15:15Z
dc.date.available
2022-12-30T04:02:59Z
dc.date.available
2022-12-30T12:15:15Z
dc.date.issued
2022-12-15
dc.identifier.issn
1932-7455
dc.identifier.issn
1932-7447
dc.identifier.other
10.1021/acs.jpcc.2c06102
en_US
dc.identifier.uri
http://hdl.handle.net/20.500.11850/589432
dc.description.abstract
The coadsorption of quinoline and hydrogen, a crucial step in the hydrogenation of quinoline, has been examined by first-principles DFT simulations using the (111) face of the catalytically essential face-centered cubic metals rhodium, palladium, platinum, and gold employed for this reaction. Special attention was given to the energetics of coadsorbed hydrogen and quinoline, the configuration of quinoline, and changes in these properties with hydrogen surface coverage and hydrogen transfer from the metal surface to quinoline. In the absence of hydrogen, quinoline is found to be chemisorbed nearly flat-lying on the surface of platinum group metals via the π-bonding system of the aromatic moiety. In contrast, the favored adsorption mode of quinoline on Au is tilted to the metal surface, and σ-bonding via the N-lone pair prevails. These binding modes are in line with the calculated Löwdin charges and projected density of states of the quinoline-metal systems. The adsorption strengths of quinoline on the pristine (111) surfaces of the metals follow the order Rh > Pd > Pt ≫ Au. The stability of the coadsorbed configurations has been analyzed in terms of the hydrogen-binding energy, showing a preference of H to bind to the N atom of quinoline on Au and Pt, while on Pd and Rh, adsorption of H atoms to the metal surface is favored. On Au, hydrogen adsorption is energetically disfavored compared to the platinum group (PG) metals. Insertion of a bulky substituent at the C4 atom of quinoline has only little influence on its energetics and adsorption configuration, as exemplified by the adsorption of cinchonidine for imparting chirality to PG metal surfaces in catalytic enantioselective hydrogenations. Possible impacts of these adsorption behaviors on the hydrogenation of quinoline and the use of the quinoline derivative cinchonidine as a chiral modifier in enantioselective hydrogenation are discussed.
en_US
dc.language.iso
en
en_US
dc.publisher
American Chemical Society
en_US
dc.title
Coadsorption and Interaction of Quinolines and Hydrogen on Platinum Group Metals and Gold: A First-Principles Analysis
en_US
dc.type
Journal Article
dc.date.published
2022-12-02
ethz.journal.title
The Journal of Physical Chemistry C
ethz.journal.volume
126
en_US
ethz.journal.issue
49
en_US
ethz.journal.abbreviated
J. Phys. Chem. C
ethz.pages.start
20840
en_US
ethz.pages.end
20851
en_US
ethz.identifier.wos
ethz.identifier.scopus
ethz.publication.place
Washington, DC
en_US
ethz.publication.status
published
en_US
ethz.date.deposited
2022-12-30T04:02:59Z
ethz.source
SCOPUS
ethz.eth
yes
en_US
ethz.availability
Metadata only
en_US
ethz.rosetta.installDate
2022-12-30T12:15:16Z
ethz.rosetta.lastUpdated
2024-02-02T19:14:22Z
ethz.rosetta.versionExported
true
ethz.COinS
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