Metastable de-excitation spectroscopy and density functional theory study of the selective oxidation of crotyl alcohol over Pd(111)

James Naughton, Andrew Pratt, Charles W. Woffinden, Christopher Eames, Steve P. Tear, Sarah M. Thompson, Adam F. Lee, Karen Wilson

Research output: Contribution to journalArticle

Abstract

The extremely surface sensitive technique of metastable de-excitation spectroscopy (MDS) has been utilized to probe the bonding and reactivity of crotyl alcohol over Pd(111) and provide insight into the selective oxidation pathway to crotonaldehyde. Auger de-excitation (AD) of metastable He (23S) atoms reveals distinct features associated with the molecular orbitals of the adsorbed alcohol, corresponding to emission from the hydrocarbon skeleton, the O n nonbonding, and C═C π states. The O n and C═C π states of the alcohol are reversed when compared to those of the aldehyde. Density functional theory (DFT) calculations of the alcohol show that an adsorption mode with both C═C and O bonds aligned somewhat parallel to the surface is energetically favored at a substrate temperature below 200 K. Density of states calculations for such configurations are in excellent agreement with experimental MDS measurements. MDS revealed oxidative dehydrogenation of crotyl alcohol to crotonaldehyde between 200 and 250 K, resulting in small peak shifts to higher binding energy. Intramolecular changes lead to the opposite assignment of the first two MOs in the alcohol versus the aldehyde, in accordance with DFT and UPS studies of the free molecules. Subsequent crotonaldehyde decarbonylation and associated propylidyne formation above 260 K could also be identified by MDS and complementary theoretical calculations as the origin of deactivation and selectivity loss. Combining MDS and DFT in this way represents a novel approach to elucidating surface catalyzed reaction pathways associated with a “real-world” practical chemical transformation, namely the selective oxidation of alcohols to aldehydes.
Original languageEnglish
Pages (from-to)25290-25297
Number of pages8
JournalJournal of Physical Chemistry: Part C
Volume115
Issue number51
Early online date28 Nov 2011
DOIs
Publication statusPublished - 29 Dec 2011

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2-butenal
Density functional theory
alcohols
Alcohols
Spectroscopy
density functional theory
Oxidation
oxidation
Aldehydes
spectroscopy
excitation
aldehydes
Surface reactions
Molecular orbitals
Dehydrogenation
Hydrocarbons
Binding energy
dehydrogenation
crotonyl alcohol
musculoskeletal system

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Naughton, James ; Pratt, Andrew ; Woffinden, Charles W. ; Eames, Christopher ; Tear, Steve P. ; Thompson, Sarah M. ; Lee, Adam F. ; Wilson, Karen. / Metastable de-excitation spectroscopy and density functional theory study of the selective oxidation of crotyl alcohol over Pd(111). In: Journal of Physical Chemistry: Part C. 2011 ; Vol. 115, No. 51. pp. 25290-25297.
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abstract = "The extremely surface sensitive technique of metastable de-excitation spectroscopy (MDS) has been utilized to probe the bonding and reactivity of crotyl alcohol over Pd(111) and provide insight into the selective oxidation pathway to crotonaldehyde. Auger de-excitation (AD) of metastable He (23S) atoms reveals distinct features associated with the molecular orbitals of the adsorbed alcohol, corresponding to emission from the hydrocarbon skeleton, the O n nonbonding, and C═C π states. The O n and C═C π states of the alcohol are reversed when compared to those of the aldehyde. Density functional theory (DFT) calculations of the alcohol show that an adsorption mode with both C═C and O bonds aligned somewhat parallel to the surface is energetically favored at a substrate temperature below 200 K. Density of states calculations for such configurations are in excellent agreement with experimental MDS measurements. MDS revealed oxidative dehydrogenation of crotyl alcohol to crotonaldehyde between 200 and 250 K, resulting in small peak shifts to higher binding energy. Intramolecular changes lead to the opposite assignment of the first two MOs in the alcohol versus the aldehyde, in accordance with DFT and UPS studies of the free molecules. Subsequent crotonaldehyde decarbonylation and associated propylidyne formation above 260 K could also be identified by MDS and complementary theoretical calculations as the origin of deactivation and selectivity loss. Combining MDS and DFT in this way represents a novel approach to elucidating surface catalyzed reaction pathways associated with a “real-world” practical chemical transformation, namely the selective oxidation of alcohols to aldehydes.",
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Naughton, J, Pratt, A, Woffinden, CW, Eames, C, Tear, SP, Thompson, SM, Lee, AF & Wilson, K 2011, 'Metastable de-excitation spectroscopy and density functional theory study of the selective oxidation of crotyl alcohol over Pd(111)', Journal of Physical Chemistry: Part C, vol. 115, no. 51, pp. 25290-25297. https://doi.org/10.1021/jp205340z

Metastable de-excitation spectroscopy and density functional theory study of the selective oxidation of crotyl alcohol over Pd(111). / Naughton, James ; Pratt, Andrew; Woffinden, Charles W.; Eames, Christopher; Tear, Steve P.; Thompson, Sarah M.; Lee, Adam F.; Wilson, Karen.

In: Journal of Physical Chemistry: Part C, Vol. 115, No. 51, 29.12.2011, p. 25290-25297.

Research output: Contribution to journalArticle

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T1 - Metastable de-excitation spectroscopy and density functional theory study of the selective oxidation of crotyl alcohol over Pd(111)

AU - Naughton, James

AU - Pratt, Andrew

AU - Woffinden, Charles W.

AU - Eames, Christopher

AU - Tear, Steve P.

AU - Thompson, Sarah M.

AU - Lee, Adam F.

AU - Wilson, Karen

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AB - The extremely surface sensitive technique of metastable de-excitation spectroscopy (MDS) has been utilized to probe the bonding and reactivity of crotyl alcohol over Pd(111) and provide insight into the selective oxidation pathway to crotonaldehyde. Auger de-excitation (AD) of metastable He (23S) atoms reveals distinct features associated with the molecular orbitals of the adsorbed alcohol, corresponding to emission from the hydrocarbon skeleton, the O n nonbonding, and C═C π states. The O n and C═C π states of the alcohol are reversed when compared to those of the aldehyde. Density functional theory (DFT) calculations of the alcohol show that an adsorption mode with both C═C and O bonds aligned somewhat parallel to the surface is energetically favored at a substrate temperature below 200 K. Density of states calculations for such configurations are in excellent agreement with experimental MDS measurements. MDS revealed oxidative dehydrogenation of crotyl alcohol to crotonaldehyde between 200 and 250 K, resulting in small peak shifts to higher binding energy. Intramolecular changes lead to the opposite assignment of the first two MOs in the alcohol versus the aldehyde, in accordance with DFT and UPS studies of the free molecules. Subsequent crotonaldehyde decarbonylation and associated propylidyne formation above 260 K could also be identified by MDS and complementary theoretical calculations as the origin of deactivation and selectivity loss. Combining MDS and DFT in this way represents a novel approach to elucidating surface catalyzed reaction pathways associated with a “real-world” practical chemical transformation, namely the selective oxidation of alcohols to aldehydes.

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