The molecular adsorption of nitrogen dioxide on Pt(111) studied by temperature programmed desorption and vibrational spectroscopy

M. E. Bartram; R. G. Windham; B. E. Koel

doi:10.1016/S0039-6028(87)80272-8

The molecular adsorption of nitrogen dioxide on Pt(111) studied by temperature programmed desorption and vibrational spectroscopy

M. E. Bartram, R. G. Windham, B. E. Koel

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Abstract

The adsorption of nitrogen dioxide (NO₂) on Pt(111) has been investigated using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS). At 100 K, NO₂ is adsorbed molecularly at all coverages to form a Pt(111) μ-N,O-nitrito surface complex. This puts NO₂ in an upright bridge-bonded configuration with C_s symmetry. Our assignment of this surface species is supported by the infrared spectrum of a μ-N,O-nitritoplatinate complex. The saturation coverage of chemisorbed NO₂ is about 0.5 monolayers (ML) at 100 K. At low coverages, θ_NO₂<0.25 ML, adsorption is irreversible and NO₂ dissociates completely by 285 K to O atoms and NO. However, at coverages greater than θ_NO₂=0.25 ML, the adsorption is partially reversible and NO₂ desorbs molecularly with first-order kinetics with E_a=19 kcal/mol. About 20% of the NO₂ adsorbs reversibly at saturation coverage. With higher exposures of NO₂, a condensed multilayer of N₂O₄ can be formed.

Original language	English (US)
Pages (from-to)	57-74
Number of pages	18
Journal	Surface Science
Volume	184
Issue number	1-2
DOIs	https://doi.org/10.1016/S0039-6028(87)80272-8
State	Published - May 2 1987
Externally published	Yes

All Science Journal Classification (ASJC) codes

Condensed Matter Physics
Surfaces and Interfaces
Surfaces, Coatings and Films
Materials Chemistry

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10.1016/S0039-6028(87)80272-8

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title = "The molecular adsorption of nitrogen dioxide on Pt(111) studied by temperature programmed desorption and vibrational spectroscopy",

abstract = "The adsorption of nitrogen dioxide (NO2) on Pt(111) has been investigated using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS). At 100 K, NO2 is adsorbed molecularly at all coverages to form a Pt(111) μ-N,O-nitrito surface complex. This puts NO2 in an upright bridge-bonded configuration with Cs symmetry. Our assignment of this surface species is supported by the infrared spectrum of a μ-N,O-nitritoplatinate complex. The saturation coverage of chemisorbed NO2 is about 0.5 monolayers (ML) at 100 K. At low coverages, θNO2<0.25 ML, adsorption is irreversible and NO2 dissociates completely by 285 K to O atoms and NO. However, at coverages greater than θNO2=0.25 ML, the adsorption is partially reversible and NO2 desorbs molecularly with first-order kinetics with Ea=19 kcal/mol. About 20% of the NO2 adsorbs reversibly at saturation coverage. With higher exposures of NO2, a condensed multilayer of N2O4 can be formed.",

author = "Bartram, {M. E.} and Windham, {R. G.} and Koel, {B. E.}",

note = "Funding Information: and AES is given with appreciation. Partial financial support for this work by the National Acid Precipitation Assessment Program and Sievers Research, Inc. is gratefully acknowledged.",

year = "1987",

month = may,

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doi = "10.1016/S0039-6028(87)80272-8",

language = "English (US)",

volume = "184",

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T1 - The molecular adsorption of nitrogen dioxide on Pt(111) studied by temperature programmed desorption and vibrational spectroscopy

AU - Bartram, M. E.

AU - Windham, R. G.

AU - Koel, B. E.

N1 - Funding Information: and AES is given with appreciation. Partial financial support for this work by the National Acid Precipitation Assessment Program and Sievers Research, Inc. is gratefully acknowledged.

PY - 1987/5/2

Y1 - 1987/5/2

N2 - The adsorption of nitrogen dioxide (NO2) on Pt(111) has been investigated using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS). At 100 K, NO2 is adsorbed molecularly at all coverages to form a Pt(111) μ-N,O-nitrito surface complex. This puts NO2 in an upright bridge-bonded configuration with Cs symmetry. Our assignment of this surface species is supported by the infrared spectrum of a μ-N,O-nitritoplatinate complex. The saturation coverage of chemisorbed NO2 is about 0.5 monolayers (ML) at 100 K. At low coverages, θNO2<0.25 ML, adsorption is irreversible and NO2 dissociates completely by 285 K to O atoms and NO. However, at coverages greater than θNO2=0.25 ML, the adsorption is partially reversible and NO2 desorbs molecularly with first-order kinetics with Ea=19 kcal/mol. About 20% of the NO2 adsorbs reversibly at saturation coverage. With higher exposures of NO2, a condensed multilayer of N2O4 can be formed.

AB - The adsorption of nitrogen dioxide (NO2) on Pt(111) has been investigated using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS). At 100 K, NO2 is adsorbed molecularly at all coverages to form a Pt(111) μ-N,O-nitrito surface complex. This puts NO2 in an upright bridge-bonded configuration with Cs symmetry. Our assignment of this surface species is supported by the infrared spectrum of a μ-N,O-nitritoplatinate complex. The saturation coverage of chemisorbed NO2 is about 0.5 monolayers (ML) at 100 K. At low coverages, θNO2<0.25 ML, adsorption is irreversible and NO2 dissociates completely by 285 K to O atoms and NO. However, at coverages greater than θNO2=0.25 ML, the adsorption is partially reversible and NO2 desorbs molecularly with first-order kinetics with Ea=19 kcal/mol. About 20% of the NO2 adsorbs reversibly at saturation coverage. With higher exposures of NO2, a condensed multilayer of N2O4 can be formed.

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JO - Surface Science

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The molecular adsorption of nitrogen dioxide on Pt(111) studied by temperature programmed desorption and vibrational spectroscopy

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