In situ infrared reflection absorption spectroscopic studies of coadsorption of CO with underpotential-deposited lead on Pt(111) in an aqueous acidic solution

Nagahiro Hoshi, Bae In Tae, Daniel Alberto Scherson

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4 Citations (Scopus)

Abstract

The effects of underpotential-deposited lead on the adsorption of CO on Pt(111) surfaces have been investigated in 0.1 M HClO4 by in situ infrared reflection absorption spectroscopy (IRAS). Lead coverages of about 0.4 on Pt(111) electrodes polarized at 0.1 V vs RHE prevent CO from adsorbing on multiply bonded sites, reducing the overall coverage to about a third of that observed in the absence of coadsorbed Pb under otherwise identical conditions, yielding a single, sharply-defined feature in the infrared reflection absorption spectra characteristic of atop-bonded CO. However, the integrated absorption band of atop CO at 0.1 V in the presence of coadsorbed Pb was found to be about 3 times higher than that predicted from the corresponding spectral features observed for Pb-free surfaces at that specific coverage corrected for dipole-dipole coupling interactions. Although much of this effect may be due to a Pb-induced decrease in the dielectric screening within the CO adlayer, the gains in intensity are too large to be explained solely on this basis, pointing to chemical factors, such as Pt-Pb charge polarization, as an important factor.

Original languageEnglish
Pages (from-to)6049-6052
Number of pages4
JournalJournal of Physical Chemistry B
Volume104
Issue number25
DOIs
Publication statusPublished - 2000 Jan 1
Externally publishedYes

Fingerprint

infrared reflection
Carbon Monoxide
Absorption spectra
Lead
dipoles
aqueous solutions
Infrared radiation
absorption spectra
Absorption spectroscopy
Screening
absorption spectroscopy
screening
Polarization
Adsorption
Electrodes
adsorption
electrodes
polarization
interactions
Spectrum Analysis

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this

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title = "In situ infrared reflection absorption spectroscopic studies of coadsorption of CO with underpotential-deposited lead on Pt(111) in an aqueous acidic solution",
abstract = "The effects of underpotential-deposited lead on the adsorption of CO on Pt(111) surfaces have been investigated in 0.1 M HClO4 by in situ infrared reflection absorption spectroscopy (IRAS). Lead coverages of about 0.4 on Pt(111) electrodes polarized at 0.1 V vs RHE prevent CO from adsorbing on multiply bonded sites, reducing the overall coverage to about a third of that observed in the absence of coadsorbed Pb under otherwise identical conditions, yielding a single, sharply-defined feature in the infrared reflection absorption spectra characteristic of atop-bonded CO. However, the integrated absorption band of atop CO at 0.1 V in the presence of coadsorbed Pb was found to be about 3 times higher than that predicted from the corresponding spectral features observed for Pb-free surfaces at that specific coverage corrected for dipole-dipole coupling interactions. Although much of this effect may be due to a Pb-induced decrease in the dielectric screening within the CO adlayer, the gains in intensity are too large to be explained solely on this basis, pointing to chemical factors, such as Pt-Pb charge polarization, as an important factor.",
author = "Nagahiro Hoshi and {In Tae}, Bae and Scherson, {Daniel Alberto}",
year = "2000",
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T1 - In situ infrared reflection absorption spectroscopic studies of coadsorption of CO with underpotential-deposited lead on Pt(111) in an aqueous acidic solution

AU - Hoshi, Nagahiro

AU - In Tae, Bae

AU - Scherson, Daniel Alberto

PY - 2000/1/1

Y1 - 2000/1/1

N2 - The effects of underpotential-deposited lead on the adsorption of CO on Pt(111) surfaces have been investigated in 0.1 M HClO4 by in situ infrared reflection absorption spectroscopy (IRAS). Lead coverages of about 0.4 on Pt(111) electrodes polarized at 0.1 V vs RHE prevent CO from adsorbing on multiply bonded sites, reducing the overall coverage to about a third of that observed in the absence of coadsorbed Pb under otherwise identical conditions, yielding a single, sharply-defined feature in the infrared reflection absorption spectra characteristic of atop-bonded CO. However, the integrated absorption band of atop CO at 0.1 V in the presence of coadsorbed Pb was found to be about 3 times higher than that predicted from the corresponding spectral features observed for Pb-free surfaces at that specific coverage corrected for dipole-dipole coupling interactions. Although much of this effect may be due to a Pb-induced decrease in the dielectric screening within the CO adlayer, the gains in intensity are too large to be explained solely on this basis, pointing to chemical factors, such as Pt-Pb charge polarization, as an important factor.

AB - The effects of underpotential-deposited lead on the adsorption of CO on Pt(111) surfaces have been investigated in 0.1 M HClO4 by in situ infrared reflection absorption spectroscopy (IRAS). Lead coverages of about 0.4 on Pt(111) electrodes polarized at 0.1 V vs RHE prevent CO from adsorbing on multiply bonded sites, reducing the overall coverage to about a third of that observed in the absence of coadsorbed Pb under otherwise identical conditions, yielding a single, sharply-defined feature in the infrared reflection absorption spectra characteristic of atop-bonded CO. However, the integrated absorption band of atop CO at 0.1 V in the presence of coadsorbed Pb was found to be about 3 times higher than that predicted from the corresponding spectral features observed for Pb-free surfaces at that specific coverage corrected for dipole-dipole coupling interactions. Although much of this effect may be due to a Pb-induced decrease in the dielectric screening within the CO adlayer, the gains in intensity are too large to be explained solely on this basis, pointing to chemical factors, such as Pt-Pb charge polarization, as an important factor.

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