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Se-C Cleavage of Hexane Selenol at Steps on Au(111)
KTH Royal Institute of Technology, Sweden.
KTH Royal Institute of Technology, Sweden.
KTH Royal Institute of Technology, Sweden.
KTH Royal Institute of Technology, Sweden.
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2018 (Engelska)Ingår i: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 34, nr 8, s. 2630-2636Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

Selenols are considered as an alternative to thiols in self-assembled monolayers, but the Se-C bond is one limiting factor for their usefulness. In this study, we address the stability of the Se-C bond by a combined experimental and theoretical investigation of gas phase-deposited hexane selenol (CH3(CH2)(5)SeH) on Au(111) using photoelectron spectroscopy, scanning tunneling microscopy, and density functional theory (DFT). Experimentally, we find that initial adsorption leaves atomic Se on the surface without any carbon left on the surface, whereas further adsorption generates a saturated selenolate layer. The Se 3d component from atomic Se appears at 0.85 eV lower binding energy than the selenolate-related component. DFT calculations show that the most stable structure of selenols on Au(111) is in the form of RSe-Au-SeR complexes adsorbed on the unreconstructed Au(111) surface. This is similar to thiols on Au(111). Calculated Se 3d core-level shifts between elemental Se and selenolate in this structure nicely reproduce the experimentally recorded shifts. Dissociation of RSeH and subsequent formation of RH are found to proceed with high barriers on defect-free Au(111) terraces, with the highest barrier for scissoring R-Se. However, at steps, these barriers are considerably lower, allowing for Se-C bond breaking and hexane desorption, leaving elemental Se at the surface. Hexane is the selenol to selenolate formed by replacing the Se-C bond with a H-C bond by using the hydrogen liberated from transformation.

Ort, förlag, år, upplaga, sidor
2018. Vol. 34, nr 8, s. 2630-2636
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Naturvetenskap
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URN: urn:nbn:se:ri:diva-33712DOI: 10.1021/acs.langmuir.7b03713Scopus ID: 2-s2.0-85042636157OAI: oai:DiVA.org:ri-33712DiVA, id: diva2:1197816
Tillgänglig från: 2018-04-14 Skapad: 2018-04-14 Senast uppdaterad: 2019-01-10Bibliografiskt granskad

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