Selective Aerobic Oxidation of Alcohols over Atomically-Dispersed Non-Precious Metal Catalysts
Abstract
Catalytic oxidation of alcohols often requires the presence of expensive transition metals. We show that earth-abundant Fe atoms dispersed throughout a nitrogen-containing carbon matrix catalyze the oxidation of benzyl alcohol and 5-hydroxymethylfurfural by O2 in the aqueous phase. Furthermore, the activity of the catalyst can be regenerated by a mild treatment in H2. An observed kinetic isotope effect indicates that β-H elimination from the alcohol is the kinetically relevant step in the mechanism, which can be accelerated by substituting Fe with Cu. Dispersed Cr, Co, and Ni also convert alcohols, demonstrating the general utility of metal–nitrogen–carbon materials for alcohol oxidation catalysis. Oxidation of aliphatic alcohols is substantially slower than that of aromatic alcohols, but adding 2,2,6,6-tetramethyl-1-piperidinyloxy as a co-catalyst with Fe can significantly improve the reaction rate.
- Authors:
-
- Univ. of Virginia, Charlottesville, VA (United States). Dept. of Chemical Engineering
- Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Chemical and Biological Engineering and Center for Microengineered Materials
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office; National Science Foundation (NSF)
- OSTI Identifier:
- 1341579
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ChemSusChem
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 2; Journal ID: ISSN 1864-5631
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; heterogeneous catalyst; N-doped carbon; non-precious metal; oxidation; reaction mechanism
Citation Formats
Xie, Jiahan, Yin, Kehua, Serov, Alexey, Artyushkova, Kateryna, Pham, Hien N., Sang, Xiahan, Unocic, Raymond R., Atanassov, Plamen, Datye, Abhaya K., and Davis, Robert J. Selective Aerobic Oxidation of Alcohols over Atomically-Dispersed Non-Precious Metal Catalysts. United States: N. p., 2016.
Web. doi:10.1002/cssc.201601364.
Xie, Jiahan, Yin, Kehua, Serov, Alexey, Artyushkova, Kateryna, Pham, Hien N., Sang, Xiahan, Unocic, Raymond R., Atanassov, Plamen, Datye, Abhaya K., & Davis, Robert J. Selective Aerobic Oxidation of Alcohols over Atomically-Dispersed Non-Precious Metal Catalysts. United States. https://doi.org/10.1002/cssc.201601364
Xie, Jiahan, Yin, Kehua, Serov, Alexey, Artyushkova, Kateryna, Pham, Hien N., Sang, Xiahan, Unocic, Raymond R., Atanassov, Plamen, Datye, Abhaya K., and Davis, Robert J. Thu .
"Selective Aerobic Oxidation of Alcohols over Atomically-Dispersed Non-Precious Metal Catalysts". United States. https://doi.org/10.1002/cssc.201601364. https://www.osti.gov/servlets/purl/1341579.
@article{osti_1341579,
title = {Selective Aerobic Oxidation of Alcohols over Atomically-Dispersed Non-Precious Metal Catalysts},
author = {Xie, Jiahan and Yin, Kehua and Serov, Alexey and Artyushkova, Kateryna and Pham, Hien N. and Sang, Xiahan and Unocic, Raymond R. and Atanassov, Plamen and Datye, Abhaya K. and Davis, Robert J.},
abstractNote = {Catalytic oxidation of alcohols often requires the presence of expensive transition metals. We show that earth-abundant Fe atoms dispersed throughout a nitrogen-containing carbon matrix catalyze the oxidation of benzyl alcohol and 5-hydroxymethylfurfural by O2 in the aqueous phase. Furthermore, the activity of the catalyst can be regenerated by a mild treatment in H2. An observed kinetic isotope effect indicates that β-H elimination from the alcohol is the kinetically relevant step in the mechanism, which can be accelerated by substituting Fe with Cu. Dispersed Cr, Co, and Ni also convert alcohols, demonstrating the general utility of metal–nitrogen–carbon materials for alcohol oxidation catalysis. Oxidation of aliphatic alcohols is substantially slower than that of aromatic alcohols, but adding 2,2,6,6-tetramethyl-1-piperidinyloxy as a co-catalyst with Fe can significantly improve the reaction rate.},
doi = {10.1002/cssc.201601364},
journal = {ChemSusChem},
number = 2,
volume = 10,
place = {United States},
year = {Thu Dec 15 00:00:00 EST 2016},
month = {Thu Dec 15 00:00:00 EST 2016}
}
Web of Science
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