Influence of oxygen and pH on the selective oxidation of ethanol on Pd catalysts

David D. Hibbitts; Matthew Neurock

doi:10.1016/j.jcat.2012.11.016

Influence of oxygen and pH on the selective oxidation of ethanol on Pd catalysts

David D. Hibbitts, Matthew Neurock

Chemical Engineering and Materials Science

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

58 Scopus citations

Abstract

The selective oxidation of ethanol on supported Pd is catalytically promoted by the presence of hydroxide species on the Pd surface as well as in solution. These hydroxide intermediates act as Brønsted bases which readily abstract protons from the hydroxyl groups of adsorbed or solution-phase alcohols. The C₁H bond of the resulting alkoxide is subsequently activated on the metal surface via hydride elimination to form acetaldehyde. Surface and solution-phase hydroxide intermediates can also readily react with the acetaldehyde via nucleophilic addition to form a germinal diol intermediate, which subsequently undergoes a second C₁H bond activation on Pd to form acetic acid. The role of O₂ is to remove the electrons produced in the oxidation reaction via the oxygen reduction reaction over Pd. The reduction reaction also regenerates the hydroxide intermediates and removes adsorbed hydrogen that is produced during the oxidation.

Original language	English (US)
Pages (from-to)	261-271
Number of pages	11
Journal	Journal of Catalysis
Volume	299
DOIs	https://doi.org/10.1016/j.jcat.2012.11.016
State	Published - Mar 2013

Bibliographical note

Funding Information:
We are grateful to the National Science Foundation for the financial support of this work through the NSF PIRE program (OISE-0730277) and NSF Center for Biorenewable Chemicals (EEC-0813570) and to the Environmental Molecular Science Laboratory, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research located at Pacific Northwest National Laboratory for supercomputing time. We would also like to thank Professor Robert J. Davis, Dr. Bhushan Zope and Ms. Sara Davis for helpful discussions.

Keywords

Alcohol oxidation
Aqueous phase
DFT
Ethanol oxidation
Pd
Solvent effects

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10.1016/j.jcat.2012.11.016

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title = "Influence of oxygen and pH on the selective oxidation of ethanol on Pd catalysts",

abstract = "The selective oxidation of ethanol on supported Pd is catalytically promoted by the presence of hydroxide species on the Pd surface as well as in solution. These hydroxide intermediates act as Br{\o}nsted bases which readily abstract protons from the hydroxyl groups of adsorbed or solution-phase alcohols. The C1H bond of the resulting alkoxide is subsequently activated on the metal surface via hydride elimination to form acetaldehyde. Surface and solution-phase hydroxide intermediates can also readily react with the acetaldehyde via nucleophilic addition to form a germinal diol intermediate, which subsequently undergoes a second C1H bond activation on Pd to form acetic acid. The role of O2 is to remove the electrons produced in the oxidation reaction via the oxygen reduction reaction over Pd. The reduction reaction also regenerates the hydroxide intermediates and removes adsorbed hydrogen that is produced during the oxidation.",

keywords = "Alcohol oxidation, Aqueous phase, DFT, Ethanol oxidation, Pd, Solvent effects",

author = "Hibbitts, {David D.} and Matthew Neurock",

note = "Funding Information: We are grateful to the National Science Foundation for the financial support of this work through the NSF PIRE program (OISE-0730277) and NSF Center for Biorenewable Chemicals (EEC-0813570) and to the Environmental Molecular Science Laboratory, a national scientific user facility sponsored by the DOE{\textquoteright}s Office of Biological and Environmental Research located at Pacific Northwest National Laboratory for supercomputing time. We would also like to thank Professor Robert J. Davis, Dr. Bhushan Zope and Ms. Sara Davis for helpful discussions.",

year = "2013",

month = mar,

doi = "10.1016/j.jcat.2012.11.016",

language = "English (US)",

volume = "299",

pages = "261--271",

journal = "Journal of Catalysis",

issn = "0021-9517",

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T1 - Influence of oxygen and pH on the selective oxidation of ethanol on Pd catalysts

AU - Hibbitts, David D.

AU - Neurock, Matthew

N1 - Funding Information: We are grateful to the National Science Foundation for the financial support of this work through the NSF PIRE program (OISE-0730277) and NSF Center for Biorenewable Chemicals (EEC-0813570) and to the Environmental Molecular Science Laboratory, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research located at Pacific Northwest National Laboratory for supercomputing time. We would also like to thank Professor Robert J. Davis, Dr. Bhushan Zope and Ms. Sara Davis for helpful discussions.

PY - 2013/3

Y1 - 2013/3

N2 - The selective oxidation of ethanol on supported Pd is catalytically promoted by the presence of hydroxide species on the Pd surface as well as in solution. These hydroxide intermediates act as Brønsted bases which readily abstract protons from the hydroxyl groups of adsorbed or solution-phase alcohols. The C1H bond of the resulting alkoxide is subsequently activated on the metal surface via hydride elimination to form acetaldehyde. Surface and solution-phase hydroxide intermediates can also readily react with the acetaldehyde via nucleophilic addition to form a germinal diol intermediate, which subsequently undergoes a second C1H bond activation on Pd to form acetic acid. The role of O2 is to remove the electrons produced in the oxidation reaction via the oxygen reduction reaction over Pd. The reduction reaction also regenerates the hydroxide intermediates and removes adsorbed hydrogen that is produced during the oxidation.

AB - The selective oxidation of ethanol on supported Pd is catalytically promoted by the presence of hydroxide species on the Pd surface as well as in solution. These hydroxide intermediates act as Brønsted bases which readily abstract protons from the hydroxyl groups of adsorbed or solution-phase alcohols. The C1H bond of the resulting alkoxide is subsequently activated on the metal surface via hydride elimination to form acetaldehyde. Surface and solution-phase hydroxide intermediates can also readily react with the acetaldehyde via nucleophilic addition to form a germinal diol intermediate, which subsequently undergoes a second C1H bond activation on Pd to form acetic acid. The role of O2 is to remove the electrons produced in the oxidation reaction via the oxygen reduction reaction over Pd. The reduction reaction also regenerates the hydroxide intermediates and removes adsorbed hydrogen that is produced during the oxidation.

KW - Alcohol oxidation

KW - Aqueous phase

KW - DFT

KW - Ethanol oxidation

KW - Pd

KW - Solvent effects

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DO - 10.1016/j.jcat.2012.11.016

M3 - Article

AN - SCOPUS:84873620830

SN - 0021-9517

VL - 299

SP - 261

EP - 271

JO - Journal of Catalysis

JF - Journal of Catalysis

ER -

Influence of oxygen and pH on the selective oxidation of ethanol on Pd catalysts

Abstract

Bibliographical note

Keywords

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