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Title: 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 O 2 in the aqueous phase. Furthermore, the activity of the catalyst can be regenerated by a mild treatment in H 2. 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:
 [1];  [1];  [2];  [2];  [2];  [3];  [3];  [2];  [2];  [1]
  1. Univ. of Virginia, Charlottesville, VA (United States). Dept. of Chemical Engineering
  2. Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Chemical and Biological Engineering and Center for Microengineered Materials
  3. 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), Fuel Cell Technologies Office (EE-3F); 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. 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., and Davis, Robert J. Thu . "Selective Aerobic Oxidation of Alcohols over Atomically-Dispersed Non-Precious Metal Catalysts". United States. doi: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 = {2016},
month = {12}
}

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Works referenced in this record:

High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline, Iron, and Cobalt
journal, April 2011


Templated bi-metallic non-PGM catalysts for oxygen reduction
journal, October 2012


Iron-Based Catalysts with Improved Oxygen Reduction Activity in Polymer Electrolyte Fuel Cells
journal, April 2009

  • Lefèvre, Michel; Proietti, Eric; Jaouen, Frédéric
  • Science, Vol. 324, Issue 5923, p. 71-74
  • DOI: 10.1126/science.1170051