Interaction of potassium with π-electron orbital containing molecules on Pt(111)

Eric Garfunkel, J. J. Maj, J. C. Frost, M. H. Farias, G. A. Somorjal

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Abstract

The interaction of coadsorbed potassium with π-orbital containing molecular adsorbates (benzene, PF3, NO, C4H8, and CH3CN) on the Pt(111) crystal face was studied by thermal desorption spectroscopy. Coadsorbed potassium significantly weakened the platinum-benzene bond. More of the benzene desorbed intact upon heating, instead of dissociating to yield H2 and surface carbon. In contrast, in previous studies it was shown that coadsorbed potassium substantially increases the platinum-carbon bond strength for adsorbed CO.1 Adsorbed NO was found to dissociate in an amount proportional to the K concentration, yielding N2 and N2O (as well as NO) in the desorption spectra. The adsorption of PF3, C4H8, and CH3CN was blocked by potassium, and no additional or shifted peaks were observed. A molecular orbital description is given to account for the potassium-induced effects. We propose that only adsorbates having molecular orbitale with energy levels located near to Ef can be significantly affected by "electronic promotion" in catalysis.

Original languageEnglish
Pages (from-to)3629-3635
Number of pages7
JournalJournal of Physical Chemistry
Volume87
Issue number19
Publication statusPublished - 1983

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electron orbitals
Potassium
potassium
Benzene
Molecules
Electrons
benzene
molecules
Adsorbates
Platinum
interactions
molecular orbitals
platinum
Carbon
desorption
Thermal desorption spectroscopy
carbon
promotion
Molecular orbitals
Electron energy levels

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Garfunkel, E., Maj, J. J., Frost, J. C., Farias, M. H., & Somorjal, G. A. (1983). Interaction of potassium with π-electron orbital containing molecules on Pt(111). Journal of Physical Chemistry, 87(19), 3629-3635.

Interaction of potassium with π-electron orbital containing molecules on Pt(111). / Garfunkel, Eric; Maj, J. J.; Frost, J. C.; Farias, M. H.; Somorjal, G. A.

In: Journal of Physical Chemistry, Vol. 87, No. 19, 1983, p. 3629-3635.

Research output: Contribution to journalArticle

Garfunkel, E, Maj, JJ, Frost, JC, Farias, MH & Somorjal, GA 1983, 'Interaction of potassium with π-electron orbital containing molecules on Pt(111)', Journal of Physical Chemistry, vol. 87, no. 19, pp. 3629-3635.
Garfunkel, Eric ; Maj, J. J. ; Frost, J. C. ; Farias, M. H. ; Somorjal, G. A. / Interaction of potassium with π-electron orbital containing molecules on Pt(111). In: Journal of Physical Chemistry. 1983 ; Vol. 87, No. 19. pp. 3629-3635.
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N2 - The interaction of coadsorbed potassium with π-orbital containing molecular adsorbates (benzene, PF3, NO, C4H8, and CH3CN) on the Pt(111) crystal face was studied by thermal desorption spectroscopy. Coadsorbed potassium significantly weakened the platinum-benzene bond. More of the benzene desorbed intact upon heating, instead of dissociating to yield H2 and surface carbon. In contrast, in previous studies it was shown that coadsorbed potassium substantially increases the platinum-carbon bond strength for adsorbed CO.1 Adsorbed NO was found to dissociate in an amount proportional to the K concentration, yielding N2 and N2O (as well as NO) in the desorption spectra. The adsorption of PF3, C4H8, and CH3CN was blocked by potassium, and no additional or shifted peaks were observed. A molecular orbital description is given to account for the potassium-induced effects. We propose that only adsorbates having molecular orbitale with energy levels located near to Ef can be significantly affected by "electronic promotion" in catalysis.

AB - The interaction of coadsorbed potassium with π-orbital containing molecular adsorbates (benzene, PF3, NO, C4H8, and CH3CN) on the Pt(111) crystal face was studied by thermal desorption spectroscopy. Coadsorbed potassium significantly weakened the platinum-benzene bond. More of the benzene desorbed intact upon heating, instead of dissociating to yield H2 and surface carbon. In contrast, in previous studies it was shown that coadsorbed potassium substantially increases the platinum-carbon bond strength for adsorbed CO.1 Adsorbed NO was found to dissociate in an amount proportional to the K concentration, yielding N2 and N2O (as well as NO) in the desorption spectra. The adsorption of PF3, C4H8, and CH3CN was blocked by potassium, and no additional or shifted peaks were observed. A molecular orbital description is given to account for the potassium-induced effects. We propose that only adsorbates having molecular orbitale with energy levels located near to Ef can be significantly affected by "electronic promotion" in catalysis.

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