Structure and decomposition pathways of vinyl acetate on Pd(1 1 1)

Florencia Calaza; Dario Stacchiola; M. Neurock; Wilfred T. Tysoe

doi:10.1016/j.susc.2005.09.028

Structure and decomposition pathways of vinyl acetate on Pd(1 1 1)

Florencia Calaza, Dario Stacchiola, M. Neurock, Wilfred T. Tysoe

Chemical Engineering and Materials Science

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36 Scopus citations

Abstract

The surface chemistry of vinyl acetate on clean Pd(1 1 1) is explored experimentally in ultrahigh vacuum using reflection absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) combined with density functional theory (DFT) calculations. The relative intensities of the vibrational features of a vinyl acetate overlayer are in good agreement with the structure calculated by DFT. Furthermore, the calculated heat of adsorption of vinyl acetate (63.4 kJ/mol) is in excellent agreement with the measured desorption activation energy (65 ± 7 kJ/mol). The thermal decomposition pathways of adsorbed vinyl acetate are relatively complex involving initial cleavage of the O-acetyl or O-vinyl bonds to form either vinyloxy and acetyl, or acetate and vinyl species, respectively on the surface. The acetate thermally decomposes to desorb methane at ∼260 K, while the acetyl and vinyloxy species isomerize and react to form acetaldehyde or methane. Ethylidyne is formed, and adsorbed CO either desorbs or oxidizes to CO₂ at ∼450 K.

Original language	English (US)
Pages (from-to)	263-275
Number of pages	13
Journal	Surface Science
Volume	598
Issue number	1-3
DOIs	https://doi.org/10.1016/j.susc.2005.09.028
State	Published - Dec 20 2005

Bibliographical note

Funding Information:
We gratefully acknowledge support of this work by the U.S. Department of Energy, Division of Chemical Sciences, Office of Basic Energy Sciences, under Grant No. DE-FG02-92ER14289.

Keywords

Infrared spectroscopy
Pd(1 1 1)
Temperature-programmed desorption
Vinyl acetate

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title = "Structure and decomposition pathways of vinyl acetate on Pd(1 1 1)",

abstract = "The surface chemistry of vinyl acetate on clean Pd(1 1 1) is explored experimentally in ultrahigh vacuum using reflection absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) combined with density functional theory (DFT) calculations. The relative intensities of the vibrational features of a vinyl acetate overlayer are in good agreement with the structure calculated by DFT. Furthermore, the calculated heat of adsorption of vinyl acetate (63.4 kJ/mol) is in excellent agreement with the measured desorption activation energy (65 ± 7 kJ/mol). The thermal decomposition pathways of adsorbed vinyl acetate are relatively complex involving initial cleavage of the O-acetyl or O-vinyl bonds to form either vinyloxy and acetyl, or acetate and vinyl species, respectively on the surface. The acetate thermally decomposes to desorb methane at ∼260 K, while the acetyl and vinyloxy species isomerize and react to form acetaldehyde or methane. Ethylidyne is formed, and adsorbed CO either desorbs or oxidizes to CO2 at ∼450 K.",

keywords = "Infrared spectroscopy, Pd(1 1 1), Temperature-programmed desorption, Vinyl acetate",

author = "Florencia Calaza and Dario Stacchiola and M. Neurock and Tysoe, {Wilfred T.}",

note = "Funding Information: We gratefully acknowledge support of this work by the U.S. Department of Energy, Division of Chemical Sciences, Office of Basic Energy Sciences, under Grant No. DE-FG02-92ER14289.",

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AU - Calaza, Florencia

AU - Stacchiola, Dario

AU - Neurock, M.

AU - Tysoe, Wilfred T.

N1 - Funding Information: We gratefully acknowledge support of this work by the U.S. Department of Energy, Division of Chemical Sciences, Office of Basic Energy Sciences, under Grant No. DE-FG02-92ER14289.

PY - 2005/12/20

Y1 - 2005/12/20

N2 - The surface chemistry of vinyl acetate on clean Pd(1 1 1) is explored experimentally in ultrahigh vacuum using reflection absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) combined with density functional theory (DFT) calculations. The relative intensities of the vibrational features of a vinyl acetate overlayer are in good agreement with the structure calculated by DFT. Furthermore, the calculated heat of adsorption of vinyl acetate (63.4 kJ/mol) is in excellent agreement with the measured desorption activation energy (65 ± 7 kJ/mol). The thermal decomposition pathways of adsorbed vinyl acetate are relatively complex involving initial cleavage of the O-acetyl or O-vinyl bonds to form either vinyloxy and acetyl, or acetate and vinyl species, respectively on the surface. The acetate thermally decomposes to desorb methane at ∼260 K, while the acetyl and vinyloxy species isomerize and react to form acetaldehyde or methane. Ethylidyne is formed, and adsorbed CO either desorbs or oxidizes to CO2 at ∼450 K.

AB - The surface chemistry of vinyl acetate on clean Pd(1 1 1) is explored experimentally in ultrahigh vacuum using reflection absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) combined with density functional theory (DFT) calculations. The relative intensities of the vibrational features of a vinyl acetate overlayer are in good agreement with the structure calculated by DFT. Furthermore, the calculated heat of adsorption of vinyl acetate (63.4 kJ/mol) is in excellent agreement with the measured desorption activation energy (65 ± 7 kJ/mol). The thermal decomposition pathways of adsorbed vinyl acetate are relatively complex involving initial cleavage of the O-acetyl or O-vinyl bonds to form either vinyloxy and acetyl, or acetate and vinyl species, respectively on the surface. The acetate thermally decomposes to desorb methane at ∼260 K, while the acetyl and vinyloxy species isomerize and react to form acetaldehyde or methane. Ethylidyne is formed, and adsorbed CO either desorbs or oxidizes to CO2 at ∼450 K.

KW - Infrared spectroscopy

KW - Pd(1 1 1)

KW - Temperature-programmed desorption

KW - Vinyl acetate

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Structure and decomposition pathways of vinyl acetate on Pd(1 1 1)

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