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. Herein, it is shown that earth-abundant Fe atoms dispersed throughout a nitrogen-containing carbon matrix catalyze the oxidation of benzyl alcohol and 5-hydroxymethylfurfural by O2in the aqueous phase. 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 addition of 2,2,6,6-tetramethyl-1-piperidinyloxy as a co-catalyst with Fe can significantly improve the reaction rate.
authors.affiliation: Department of Chemical Engineering, University of Virginia, Charlottesville, VA, 22904, USA.
authors.forename: Jiahan
authors.initials: J
authors.lastname: Xie
authors.affiliation: Department of Chemical Engineering, University of Virginia, Charlottesville, VA, 22904, USA.
authors.forename: Kehua
authors.initials: K
authors.lastname: Yin
authors.affiliation: Department of Chemical and Biological Engineering and Center for Micro-engineered Materials, University of New Mexico, Albuquerque, NM, 87131, USA.
authors.forename: Alexey
authors.initials: A
authors.lastname: Serov
authors.affiliation: Department of Chemical and Biological Engineering and Center for Micro-engineered Materials, University of New Mexico, Albuquerque, NM, 87131, USA.
authors.forename: Kateryna
authors.initials: K
authors.lastname: Artyushkova
authors.affiliation: Department of Chemical and Biological Engineering and Center for Micro-engineered Materials, University of New Mexico, Albuquerque, NM, 87131, USA.
authors.forename: Hien N
authors.initials: HN
authors.lastname: Pham
authors.affiliation: Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN, 37831, USA.
authors.forename: Xiahan
authors.initials: X
authors.lastname: Sang
authors.affiliation: Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN, 37831, USA.
authors.forename: Raymond R
authors.initials: RR
authors.lastname: Unocic
authors.affiliation: Department of Chemical and Biological Engineering and Center for Micro-engineered Materials, University of New Mexico, Albuquerque, NM, 87131, USA.
authors.forename: Plamen
authors.initials: P
authors.lastname: Atanassov
authors.affiliation: Department of Chemical and Biological Engineering and Center for Micro-engineered Materials, University of New Mexico, Albuquerque, NM, 87131, USA.
authors.forename: Abhaya K
authors.initials: AK
authors.lastname: Datye
authors.affiliation: Department of Chemical Engineering, University of Virginia, 102 Engineers' Way, Charlottesville, VA, 22904, USA.
authors.forename: Robert J
authors.initials: RJ
authors.lastname: Davis
mesh_terms: D019905:Benzyl Alcohol / Q000737:chemistry*; D002384:Catalysis; D005662:Furaldehyde / Q000031:analogs & derivatives / Q000737:chemistry; D007501:Iron / Q000737:chemistry*; D007700:Kinetics; D009584:Nitrogen / Q000737:chemistry; D010084:Oxidation-Reduction; D014867:Water / Q000737:chemistry
chemical_list: D014867:Water; C008046:5-hydroxymethylfurfural; D005662:Furaldehyde; D007501:Iron; D019905:Benzyl Alcohol; D009584:Nitrogen
keywords: N-doped carbon; heterogeneous catalyst; non-precious metal; oxidation; reaction mechanism