Chemically diverse environmental interfaces and their reactions with ozone studied by sum frequency generation

Grace Y. Stokes; Avram M. Buchbinder; Julianne M. Gibbs-Davis; Karl A. Scheidt; Franz M. Geiger

doi:10.1016/j.vibspec.2008.08.003

Chemically diverse environmental interfaces and their reactions with ozone studied by sum frequency generation

Grace Y. Stokes, Avram M. Buchbinder, Julianne M. Gibbs-Davis, Karl A. Scheidt, Franz M. Geiger^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

34 Scopus citations

Abstract

Using tailor-made organic compounds tethered to solid substrates through organo-silane chemistry, we present a reductionist model study aimed at understanding the mechanisms of heterogeneous organic oxidation reactions at solid/air interfaces. The surface vibrational spectra of glass slides functionalized with the tropospherically relevant olefins 1-pentene, 2-hexene, cyclopentene, cyclohexene, and a menthenol derivative via aniline-silane linkers have been obtained through polarization-resolved broadband vibrational sum frequency generation (SFG). The olefinic and aliphatic CH stretches located above and below 3000 cm^-1, respectively, are clearly discernable and their spectral intensities are used to track, with 10 s time resolution, C{double bond, long}C double bond oxidation reactions of surface-bound cyclohexene at room temperature and with low ppm amounts of ozone at 1 atm. The olefinic CH stretching mode disappears at a rate of 0.05(1) s^-1, and the aliphatic asymmetric stretch modes increase at a rate of 0.04(1) s^-1. Analogous experiments show the formation of methyl groups even for those olefins under investigation that do not originally possess methyl groups. The implications for heterogeneous organic oxidation chemistry involving tropospheric dust particles are discussed.

Original language	English (US)
Pages (from-to)	86-98
Number of pages	13
Journal	Vibrational Spectroscopy
Volume	50
Issue number	1
DOIs	https://doi.org/10.1016/j.vibspec.2008.08.003
State	Published - May 26 2009

Funding

GYS gratefully acknowledges support by NASA Headquarters under the NASA Earth and Space Science Fellowship program (Grant 07-Earth07R-0084). JMG-D gratefully acknowledges a fellowship from the Camille and Henry Dreyfus Postdoctoral Program in Environmental Chemistry. Support for this project is provided by the National Science Foundation Atmospheric Chemistry division and the ACS Petroleum Research Fund. This work was supported by the Director, Chemical Sciences, Geosciences and Biosciences Division, of the U.S. Department of Energy as well as the National Science Foundation CAREER grant in Experimental Physical Chemistry. Support from the DOE-funded Northwestern University Institute for Catalysis in Energy Processes (ICEP) and the Northwestern University International Institute for Nanotechnology (IIN) is greatly appreciated. We thank Mark A. Anderson and Professor R.P.H. Chang for ellipsometry analysis. The authors also acknowledge donations, equipment loans and the technical support of Spectra Physics, a Division of Newport Corporation, and helpful discussions with Dr. Michael J. Musorrafiti. FMG is the Northwestern University Dow Chemical Company professor. KAS and FMG are both Sloan Foundation Fellows.

Keywords

Cyclohexane
Cyclohexene
Cyclopentene
Hexene
Olefins
Ozone
Pentene
Sum frequency generation
Terpene
Tropospheric chemistry

ASJC Scopus subject areas

Spectroscopy

Access to Document

10.1016/j.vibspec.2008.08.003

Cite this

@article{480c8d61a889433d9e0a8ddd0e0c8b2c,

title = "Chemically diverse environmental interfaces and their reactions with ozone studied by sum frequency generation",

abstract = "Using tailor-made organic compounds tethered to solid substrates through organo-silane chemistry, we present a reductionist model study aimed at understanding the mechanisms of heterogeneous organic oxidation reactions at solid/air interfaces. The surface vibrational spectra of glass slides functionalized with the tropospherically relevant olefins 1-pentene, 2-hexene, cyclopentene, cyclohexene, and a menthenol derivative via aniline-silane linkers have been obtained through polarization-resolved broadband vibrational sum frequency generation (SFG). The olefinic and aliphatic CH stretches located above and below 3000 cm-1, respectively, are clearly discernable and their spectral intensities are used to track, with 10 s time resolution, C{double bond, long}C double bond oxidation reactions of surface-bound cyclohexene at room temperature and with low ppm amounts of ozone at 1 atm. The olefinic CH stretching mode disappears at a rate of 0.05(1) s-1, and the aliphatic asymmetric stretch modes increase at a rate of 0.04(1) s-1. Analogous experiments show the formation of methyl groups even for those olefins under investigation that do not originally possess methyl groups. The implications for heterogeneous organic oxidation chemistry involving tropospheric dust particles are discussed.",

keywords = "Cyclohexane, Cyclohexene, Cyclopentene, Hexene, Olefins, Ozone, Pentene, Sum frequency generation, Terpene, Tropospheric chemistry",

author = "Stokes, {Grace Y.} and Buchbinder, {Avram M.} and Gibbs-Davis, {Julianne M.} and Scheidt, {Karl A.} and Geiger, {Franz M.}",

note = "Funding Information: GYS gratefully acknowledges support by NASA Headquarters under the NASA Earth and Space Science Fellowship program (Grant 07-Earth07R-0084). JMG-D gratefully acknowledges a fellowship from the Camille and Henry Dreyfus Postdoctoral Program in Environmental Chemistry. Support for this project is provided by the National Science Foundation Atmospheric Chemistry division and the ACS Petroleum Research Fund. This work was supported by the Director, Chemical Sciences, Geosciences and Biosciences Division, of the U.S. Department of Energy as well as the National Science Foundation CAREER grant in Experimental Physical Chemistry. Support from the DOE-funded Northwestern University Institute for Catalysis in Energy Processes (ICEP) and the Northwestern University International Institute for Nanotechnology (IIN) is greatly appreciated. We thank Mark A. Anderson and Professor R.P.H. Chang for ellipsometry analysis. The authors also acknowledge donations, equipment loans and the technical support of Spectra Physics, a Division of Newport Corporation, and helpful discussions with Dr. Michael J. Musorrafiti. FMG is the Northwestern University Dow Chemical Company professor. KAS and FMG are both Sloan Foundation Fellows.",

year = "2009",

month = may,

day = "26",

doi = "10.1016/j.vibspec.2008.08.003",

language = "English (US)",

volume = "50",

pages = "86--98",

journal = "Vibrational Spectroscopy",

issn = "0924-2031",

publisher = "Elsevier B.V.",

number = "1",

}

TY - JOUR

T1 - Chemically diverse environmental interfaces and their reactions with ozone studied by sum frequency generation

AU - Stokes, Grace Y.

AU - Buchbinder, Avram M.

AU - Gibbs-Davis, Julianne M.

AU - Scheidt, Karl A.

AU - Geiger, Franz M.

N1 - Funding Information: GYS gratefully acknowledges support by NASA Headquarters under the NASA Earth and Space Science Fellowship program (Grant 07-Earth07R-0084). JMG-D gratefully acknowledges a fellowship from the Camille and Henry Dreyfus Postdoctoral Program in Environmental Chemistry. Support for this project is provided by the National Science Foundation Atmospheric Chemistry division and the ACS Petroleum Research Fund. This work was supported by the Director, Chemical Sciences, Geosciences and Biosciences Division, of the U.S. Department of Energy as well as the National Science Foundation CAREER grant in Experimental Physical Chemistry. Support from the DOE-funded Northwestern University Institute for Catalysis in Energy Processes (ICEP) and the Northwestern University International Institute for Nanotechnology (IIN) is greatly appreciated. We thank Mark A. Anderson and Professor R.P.H. Chang for ellipsometry analysis. The authors also acknowledge donations, equipment loans and the technical support of Spectra Physics, a Division of Newport Corporation, and helpful discussions with Dr. Michael J. Musorrafiti. FMG is the Northwestern University Dow Chemical Company professor. KAS and FMG are both Sloan Foundation Fellows.

PY - 2009/5/26

Y1 - 2009/5/26

N2 - Using tailor-made organic compounds tethered to solid substrates through organo-silane chemistry, we present a reductionist model study aimed at understanding the mechanisms of heterogeneous organic oxidation reactions at solid/air interfaces. The surface vibrational spectra of glass slides functionalized with the tropospherically relevant olefins 1-pentene, 2-hexene, cyclopentene, cyclohexene, and a menthenol derivative via aniline-silane linkers have been obtained through polarization-resolved broadband vibrational sum frequency generation (SFG). The olefinic and aliphatic CH stretches located above and below 3000 cm-1, respectively, are clearly discernable and their spectral intensities are used to track, with 10 s time resolution, C{double bond, long}C double bond oxidation reactions of surface-bound cyclohexene at room temperature and with low ppm amounts of ozone at 1 atm. The olefinic CH stretching mode disappears at a rate of 0.05(1) s-1, and the aliphatic asymmetric stretch modes increase at a rate of 0.04(1) s-1. Analogous experiments show the formation of methyl groups even for those olefins under investigation that do not originally possess methyl groups. The implications for heterogeneous organic oxidation chemistry involving tropospheric dust particles are discussed.

AB - Using tailor-made organic compounds tethered to solid substrates through organo-silane chemistry, we present a reductionist model study aimed at understanding the mechanisms of heterogeneous organic oxidation reactions at solid/air interfaces. The surface vibrational spectra of glass slides functionalized with the tropospherically relevant olefins 1-pentene, 2-hexene, cyclopentene, cyclohexene, and a menthenol derivative via aniline-silane linkers have been obtained through polarization-resolved broadband vibrational sum frequency generation (SFG). The olefinic and aliphatic CH stretches located above and below 3000 cm-1, respectively, are clearly discernable and their spectral intensities are used to track, with 10 s time resolution, C{double bond, long}C double bond oxidation reactions of surface-bound cyclohexene at room temperature and with low ppm amounts of ozone at 1 atm. The olefinic CH stretching mode disappears at a rate of 0.05(1) s-1, and the aliphatic asymmetric stretch modes increase at a rate of 0.04(1) s-1. Analogous experiments show the formation of methyl groups even for those olefins under investigation that do not originally possess methyl groups. The implications for heterogeneous organic oxidation chemistry involving tropospheric dust particles are discussed.

KW - Cyclohexane

KW - Cyclohexene

KW - Cyclopentene

KW - Hexene

KW - Olefins

KW - Ozone

KW - Pentene

KW - Sum frequency generation

KW - Terpene

KW - Tropospheric chemistry

UR - http://www.scopus.com/inward/record.url?scp=67349230322&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=67349230322&partnerID=8YFLogxK

U2 - 10.1016/j.vibspec.2008.08.003

DO - 10.1016/j.vibspec.2008.08.003

M3 - Article

AN - SCOPUS:67349230322

SN - 0924-2031

VL - 50

SP - 86

EP - 98

JO - Vibrational Spectroscopy

JF - Vibrational Spectroscopy

IS - 1

ER -

Chemically diverse environmental interfaces and their reactions with ozone studied by sum frequency generation

Abstract

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this