Adsorption of CN at the Pt(111)/Liquid Interface by Dissociation of Acetonitrile and the Potentiality of CO Contamination: A Sum-Frequency Generation Study

F. Dederichs, Anna Petoukhova, W. Daum

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Abstract

The adsorption of cyanide, CN, on the Pt(111) surface by dissociation of acetonitrile, CH3CN, has been investigated by sum-frequency generation (SFG) as surface vibrational spectroscopy and by cyclic voltammetry. The adsorption procedure involved cooling of the flame-annealed Pt crystal above a dilute aqueous solution of acetonitrile (0.1 M HClO4 + 0.025 M CH3CN), followed by immersion of the sample into the electrolyte. The adsorbed species is identified as cyanide by the characteristic potential dependence of the stretching frequency, which increased from 2087 cm-1 at 0.1 V to 2136 cm-1 at 0.95 V, as well as by cyclic voltammetry. Comparison with the voltammogram in a 1 × 10-3 M solution of CH3CN indicates that the dissociation takes place in the gas phase above the solution. A second band in our spectra with a frequency near 2155 cm-1 is tentatively assigned to a Pt−cyano surface complex. We also report on experiments in which the same annealing/cooling procedure has been applied using neat liquid acetonitrile. Bands near 1860 and 2073 cm-1 in SFG spectra of these samples are shown to originate from adsorbed CO, most likely produced by oxidation of CH3CN vapor at the hot Pt crystal. CN adsorption at the Pt(111)/liquid acetonitrile interface, performed by deposition of cyanide ions from solutions of tetrabutylammonium cyanide in acetonitrile, is characterized by a single band near 2110 cm-1.
Original languageEnglish
Pages (from-to)5210-5216
Number of pages7
JournalJournal of physical chemistry B
Volume105
Issue number22
DOIs
Publication statusPublished - 2001

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Carbon Monoxide
Acetonitrile
acetonitrile
Cyanides
cyanides
contamination
Contamination
dissociation
Adsorption
adsorption
Liquids
liquids
Cyclic voltammetry
Cooling
cooling
Vibrational spectroscopy
Crystals
submerging
Electrolytes
Stretching

Keywords

  • METIS-200191
  • IR-96462

Cite this

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title = "Adsorption of CN at the Pt(111)/Liquid Interface by Dissociation of Acetonitrile and the Potentiality of CO Contamination: A Sum-Frequency Generation Study",
abstract = "The adsorption of cyanide, CN, on the Pt(111) surface by dissociation of acetonitrile, CH3CN, has been investigated by sum-frequency generation (SFG) as surface vibrational spectroscopy and by cyclic voltammetry. The adsorption procedure involved cooling of the flame-annealed Pt crystal above a dilute aqueous solution of acetonitrile (0.1 M HClO4 + 0.025 M CH3CN), followed by immersion of the sample into the electrolyte. The adsorbed species is identified as cyanide by the characteristic potential dependence of the stretching frequency, which increased from 2087 cm-1 at 0.1 V to 2136 cm-1 at 0.95 V, as well as by cyclic voltammetry. Comparison with the voltammogram in a 1 × 10-3 M solution of CH3CN indicates that the dissociation takes place in the gas phase above the solution. A second band in our spectra with a frequency near 2155 cm-1 is tentatively assigned to a Pt−cyano surface complex. We also report on experiments in which the same annealing/cooling procedure has been applied using neat liquid acetonitrile. Bands near 1860 and 2073 cm-1 in SFG spectra of these samples are shown to originate from adsorbed CO, most likely produced by oxidation of CH3CN vapor at the hot Pt crystal. CN adsorption at the Pt(111)/liquid acetonitrile interface, performed by deposition of cyanide ions from solutions of tetrabutylammonium cyanide in acetonitrile, is characterized by a single band near 2110 cm-1.",
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author = "F. Dederichs and Anna Petoukhova and W. Daum",
year = "2001",
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language = "English",
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Adsorption of CN at the Pt(111)/Liquid Interface by Dissociation of Acetonitrile and the Potentiality of CO Contamination: A Sum-Frequency Generation Study. / Dederichs, F.; Petoukhova, Anna; Daum, W.

In: Journal of physical chemistry B, Vol. 105, No. 22, 2001, p. 5210-5216.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Adsorption of CN at the Pt(111)/Liquid Interface by Dissociation of Acetonitrile and the Potentiality of CO Contamination: A Sum-Frequency Generation Study

AU - Dederichs, F.

AU - Petoukhova, Anna

AU - Daum, W.

PY - 2001

Y1 - 2001

N2 - The adsorption of cyanide, CN, on the Pt(111) surface by dissociation of acetonitrile, CH3CN, has been investigated by sum-frequency generation (SFG) as surface vibrational spectroscopy and by cyclic voltammetry. The adsorption procedure involved cooling of the flame-annealed Pt crystal above a dilute aqueous solution of acetonitrile (0.1 M HClO4 + 0.025 M CH3CN), followed by immersion of the sample into the electrolyte. The adsorbed species is identified as cyanide by the characteristic potential dependence of the stretching frequency, which increased from 2087 cm-1 at 0.1 V to 2136 cm-1 at 0.95 V, as well as by cyclic voltammetry. Comparison with the voltammogram in a 1 × 10-3 M solution of CH3CN indicates that the dissociation takes place in the gas phase above the solution. A second band in our spectra with a frequency near 2155 cm-1 is tentatively assigned to a Pt−cyano surface complex. We also report on experiments in which the same annealing/cooling procedure has been applied using neat liquid acetonitrile. Bands near 1860 and 2073 cm-1 in SFG spectra of these samples are shown to originate from adsorbed CO, most likely produced by oxidation of CH3CN vapor at the hot Pt crystal. CN adsorption at the Pt(111)/liquid acetonitrile interface, performed by deposition of cyanide ions from solutions of tetrabutylammonium cyanide in acetonitrile, is characterized by a single band near 2110 cm-1.

AB - The adsorption of cyanide, CN, on the Pt(111) surface by dissociation of acetonitrile, CH3CN, has been investigated by sum-frequency generation (SFG) as surface vibrational spectroscopy and by cyclic voltammetry. The adsorption procedure involved cooling of the flame-annealed Pt crystal above a dilute aqueous solution of acetonitrile (0.1 M HClO4 + 0.025 M CH3CN), followed by immersion of the sample into the electrolyte. The adsorbed species is identified as cyanide by the characteristic potential dependence of the stretching frequency, which increased from 2087 cm-1 at 0.1 V to 2136 cm-1 at 0.95 V, as well as by cyclic voltammetry. Comparison with the voltammogram in a 1 × 10-3 M solution of CH3CN indicates that the dissociation takes place in the gas phase above the solution. A second band in our spectra with a frequency near 2155 cm-1 is tentatively assigned to a Pt−cyano surface complex. We also report on experiments in which the same annealing/cooling procedure has been applied using neat liquid acetonitrile. Bands near 1860 and 2073 cm-1 in SFG spectra of these samples are shown to originate from adsorbed CO, most likely produced by oxidation of CH3CN vapor at the hot Pt crystal. CN adsorption at the Pt(111)/liquid acetonitrile interface, performed by deposition of cyanide ions from solutions of tetrabutylammonium cyanide in acetonitrile, is characterized by a single band near 2110 cm-1.

KW - METIS-200191

KW - IR-96462

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M3 - Article

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SP - 5210

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JO - Journal of physical chemistry B

JF - Journal of physical chemistry B

SN - 1520-6106

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ER -