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Title: Selective Aerobic Oxidation of Alcohols over Atomically-Dispersed Non-Precious Metal Catalysts

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.
 [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:
Grant/Contract Number:
Accepted Manuscript
Journal Name:
Additional Journal Information:
Journal Volume: 10; Journal Issue: 2; Journal ID: ISSN 1864-5631
ChemPubSoc Europe
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)
Country of Publication:
United States
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; heterogeneous catalyst; N-doped carbon; non-precious metal; oxidation; reaction mechanism
OSTI Identifier: