Electrochemical oxidation of adsorbed terminal alkenols as afunction of chain length at Pt (111) electrodes. Studies by cyclic voltanunetry, EELS, and Auger spectroscopy

Scott A. Chaffins, John Y. Gui, Chiu-Hsun Lin, Frank Lu, Ghaleb N. Salaita, Donald A. Stem, Bruce E. Kahn, Arthur T. Hubbard

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

Reported are studies of adsorption and electrochemical oxidation of a series of straight-chain terminal alkenols at a Pt (111) electrode surface. Vibrational spectra of each adsorbed layer were obtained by use of electron energy-loss spectroscopy (EELS). Molecular packing density in the adsorbed layer was measured by means of Auger electron spectroscopy. Substrate surface structure was monitored by use of LEED. Electrochemical oxidation of each adsorbed layer was explored by means of linear potential scan voltammetry in an inert aqueous electrolyte (KF+HF). Compounds studied are: 2-propen-1-ol (PPEOH, allyl alcohol); 3-buten-1-ol (BTEOH); 4-penten-1-ol (PTEOH); 5-hexen-l-ol (HXEOH); and 10-undecen-1-ol (UDEOH). Attachment to the surface is primarily through the CC double bond. Regardless of chain length each chemisorbed aLkenol molecule occupies an area similar to that of PPEOH. EELS spectra indicate that the CC double bond is preserved in the adsorbed state. Evidently, the CC axis is parallel to the Pt (111) surface, and the alphatic chain is pendant. The -OH moiety is in contact with the Pt surface only in the case of PPEOH. An O-H stretching band is present only in the EELS spectrum of BTEOH; intermolecular hydrdogen bonding (PTEOH, HXEOH, UDEOH) and interaction with the Pt surface (PPEOH) eliminate the O-H stretching bands of the other adsorbed terminal alkenols studied. Measurement of the average number of electrons, nox required for catalytic electrocheroical oxidation of an adsorbed molecule reveals that oxidation takes place primarily at the CC double bond and one adjacent saturated carbon.

Original languageEnglish
Pages (from-to)67-80
Number of pages14
JournalJournal of Electroanalytical Chemistry
Volume284
Issue number1
DOIs
Publication statusPublished - 1990 May 10

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Electrochemical oxidation
Electron energy loss spectroscopy
Chain length
Spectroscopy
Electrodes
Stretching
Molecules
Catalytic oxidation
Vibrational spectra
Auger electron spectroscopy
Voltammetry
Surface structure
Electrolytes
Alcohols
Carbon
Adsorption
Oxidation
Electrons
Substrates
allyl alcohol

All Science Journal Classification (ASJC) codes

  • Analytical Chemistry
  • Chemical Engineering(all)
  • Electrochemistry

Cite this

Chaffins, Scott A. ; Gui, John Y. ; Lin, Chiu-Hsun ; Lu, Frank ; Salaita, Ghaleb N. ; Stem, Donald A. ; Kahn, Bruce E. ; Hubbard, Arthur T. / Electrochemical oxidation of adsorbed terminal alkenols as afunction of chain length at Pt (111) electrodes. Studies by cyclic voltanunetry, EELS, and Auger spectroscopy. In: Journal of Electroanalytical Chemistry. 1990 ; Vol. 284, No. 1. pp. 67-80.
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abstract = "Reported are studies of adsorption and electrochemical oxidation of a series of straight-chain terminal alkenols at a Pt (111) electrode surface. Vibrational spectra of each adsorbed layer were obtained by use of electron energy-loss spectroscopy (EELS). Molecular packing density in the adsorbed layer was measured by means of Auger electron spectroscopy. Substrate surface structure was monitored by use of LEED. Electrochemical oxidation of each adsorbed layer was explored by means of linear potential scan voltammetry in an inert aqueous electrolyte (KF+HF). Compounds studied are: 2-propen-1-ol (PPEOH, allyl alcohol); 3-buten-1-ol (BTEOH); 4-penten-1-ol (PTEOH); 5-hexen-l-ol (HXEOH); and 10-undecen-1-ol (UDEOH). Attachment to the surface is primarily through the CC double bond. Regardless of chain length each chemisorbed aLkenol molecule occupies an area similar to that of PPEOH. EELS spectra indicate that the CC double bond is preserved in the adsorbed state. Evidently, the CC axis is parallel to the Pt (111) surface, and the alphatic chain is pendant. The -OH moiety is in contact with the Pt surface only in the case of PPEOH. An O-H stretching band is present only in the EELS spectrum of BTEOH; intermolecular hydrdogen bonding (PTEOH, HXEOH, UDEOH) and interaction with the Pt surface (PPEOH) eliminate the O-H stretching bands of the other adsorbed terminal alkenols studied. Measurement of the average number of electrons, nox required for catalytic electrocheroical oxidation of an adsorbed molecule reveals that oxidation takes place primarily at the CC double bond and one adjacent saturated carbon.",
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Electrochemical oxidation of adsorbed terminal alkenols as afunction of chain length at Pt (111) electrodes. Studies by cyclic voltanunetry, EELS, and Auger spectroscopy. / Chaffins, Scott A.; Gui, John Y.; Lin, Chiu-Hsun; Lu, Frank; Salaita, Ghaleb N.; Stem, Donald A.; Kahn, Bruce E.; Hubbard, Arthur T.

In: Journal of Electroanalytical Chemistry, Vol. 284, No. 1, 10.05.1990, p. 67-80.

Research output: Contribution to journalArticle

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T1 - Electrochemical oxidation of adsorbed terminal alkenols as afunction of chain length at Pt (111) electrodes. Studies by cyclic voltanunetry, EELS, and Auger spectroscopy

AU - Chaffins, Scott A.

AU - Gui, John Y.

AU - Lin, Chiu-Hsun

AU - Lu, Frank

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AU - Kahn, Bruce E.

AU - Hubbard, Arthur T.

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N2 - Reported are studies of adsorption and electrochemical oxidation of a series of straight-chain terminal alkenols at a Pt (111) electrode surface. Vibrational spectra of each adsorbed layer were obtained by use of electron energy-loss spectroscopy (EELS). Molecular packing density in the adsorbed layer was measured by means of Auger electron spectroscopy. Substrate surface structure was monitored by use of LEED. Electrochemical oxidation of each adsorbed layer was explored by means of linear potential scan voltammetry in an inert aqueous electrolyte (KF+HF). Compounds studied are: 2-propen-1-ol (PPEOH, allyl alcohol); 3-buten-1-ol (BTEOH); 4-penten-1-ol (PTEOH); 5-hexen-l-ol (HXEOH); and 10-undecen-1-ol (UDEOH). Attachment to the surface is primarily through the CC double bond. Regardless of chain length each chemisorbed aLkenol molecule occupies an area similar to that of PPEOH. EELS spectra indicate that the CC double bond is preserved in the adsorbed state. Evidently, the CC axis is parallel to the Pt (111) surface, and the alphatic chain is pendant. The -OH moiety is in contact with the Pt surface only in the case of PPEOH. An O-H stretching band is present only in the EELS spectrum of BTEOH; intermolecular hydrdogen bonding (PTEOH, HXEOH, UDEOH) and interaction with the Pt surface (PPEOH) eliminate the O-H stretching bands of the other adsorbed terminal alkenols studied. Measurement of the average number of electrons, nox required for catalytic electrocheroical oxidation of an adsorbed molecule reveals that oxidation takes place primarily at the CC double bond and one adjacent saturated carbon.

AB - Reported are studies of adsorption and electrochemical oxidation of a series of straight-chain terminal alkenols at a Pt (111) electrode surface. Vibrational spectra of each adsorbed layer were obtained by use of electron energy-loss spectroscopy (EELS). Molecular packing density in the adsorbed layer was measured by means of Auger electron spectroscopy. Substrate surface structure was monitored by use of LEED. Electrochemical oxidation of each adsorbed layer was explored by means of linear potential scan voltammetry in an inert aqueous electrolyte (KF+HF). Compounds studied are: 2-propen-1-ol (PPEOH, allyl alcohol); 3-buten-1-ol (BTEOH); 4-penten-1-ol (PTEOH); 5-hexen-l-ol (HXEOH); and 10-undecen-1-ol (UDEOH). Attachment to the surface is primarily through the CC double bond. Regardless of chain length each chemisorbed aLkenol molecule occupies an area similar to that of PPEOH. EELS spectra indicate that the CC double bond is preserved in the adsorbed state. Evidently, the CC axis is parallel to the Pt (111) surface, and the alphatic chain is pendant. The -OH moiety is in contact with the Pt surface only in the case of PPEOH. An O-H stretching band is present only in the EELS spectrum of BTEOH; intermolecular hydrdogen bonding (PTEOH, HXEOH, UDEOH) and interaction with the Pt surface (PPEOH) eliminate the O-H stretching bands of the other adsorbed terminal alkenols studied. Measurement of the average number of electrons, nox required for catalytic electrocheroical oxidation of an adsorbed molecule reveals that oxidation takes place primarily at the CC double bond and one adjacent saturated carbon.

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