DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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 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:
 [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), 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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 58 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Recent Advances in Immobilized Metal Catalysts for Environmentally Benign Oxidation of Alcohols
journal, February 2008

  • Matsumoto, Tsutomu; Ueno, Masaharu; Wang, Naiwei
  • Chemistry - An Asian Journal, Vol. 3, Issue 2
  • DOI: 10.1002/asia.200700359

Addressing the terawatt challenge: scalability in the supply of chemical elements for renewable energy
journal, January 2012

  • Vesborg, Peter C. K.; Jaramillo, Thomas F.
  • RSC Advances, Vol. 2, Issue 21
  • DOI: 10.1039/c2ra20839c

Aerobic oxidation catalysis with stable radicals
journal, January 2014

  • Cao, Qun; Dornan, Laura M.; Rogan, Luke
  • Chem. Commun., Vol. 50, Issue 35
  • DOI: 10.1039/C3CC47081D

Tuning Catalytic Activity between Homogeneous and Heterogeneous Catalysis: Improved Activity and Selectivity of Free Nano-Fe2O3 in Selective Oxidations
journal, November 2007

  • Shi, Feng; Tse, Man Kin; Pohl, Marga-Matina
  • Angewandte Chemie, Vol. 119, Issue 46
  • DOI: 10.1002/ange.200703418

Layered-Carbon-Stabilized Iron Oxide Nanostructures as Oxidation Catalysts
journal, August 2011

  • Gao, Yongjun; Ma, Ding; Hu, Gang
  • Angewandte Chemie International Edition, Vol. 50, Issue 43
  • DOI: 10.1002/anie.201101737

A Graphene Composite Material with Single Cobalt Active Sites: A Highly Efficient Counter Electrode for Dye-Sensitized Solar Cells
journal, April 2016


Nano-structured non-platinum catalysts for automotive fuel cell application
journal, September 2015


Unravelling the Structure of Electrocatalytically Active Fe-N Complexes in Carbon for the Oxygen Reduction Reaction
journal, August 2014


Critical role of intercalated water for electrocatalytically active nitrogen-doped graphitic systems
journal, March 2016

  • Martinez, Ulises; Dumont, Joseph H.; Holby, Edward F.
  • Science Advances, Vol. 2, Issue 3
  • DOI: 10.1126/sciadv.1501178

Mesoporous Metal–Nitrogen-Doped Carbon Electrocatalysts for Highly Efficient Oxygen Reduction Reaction
journal, October 2013

  • Liang, Hai-Wei; Wei, Wei; Wu, Zhong-Shuai
  • Journal of the American Chemical Society, Vol. 135, Issue 43
  • DOI: 10.1021/ja407552k

On the Role of Metals in Nitrogen-Doped Carbon Electrocatalysts for Oxygen Reduction
journal, July 2015

  • Masa, Justus; Xia, Wei; Muhler, Martin
  • Angewandte Chemie International Edition, Vol. 54, Issue 35
  • DOI: 10.1002/anie.201500569

Bio-inspired design of electrocatalysts for oxalate oxidation: a combined experimental and computational study of Mn–N–C catalysts
journal, January 2015

  • Matanovic, Ivana; Babanova, Sofia; Perry III, Albert
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 20
  • DOI: 10.1039/C5CP00676G

Rational design of carbon support to prepare ultrafine iron oxide catalysts for air oxidation of alcohols
journal, January 2015

  • Geng, Longlong; Zhang, Min; Zhang, Wenxiang
  • Catalysis Science & Technology, Vol. 5, Issue 6
  • DOI: 10.1039/C5CY00022J

Selective oxidation of alcohols and aldehydes over supported metal nanoparticles
journal, January 2013

  • Davis, Sara E.; Ide, Matthew S.; Davis, Robert J.
  • Green Chem., Vol. 15, Issue 1
  • DOI: 10.1039/C2GC36441G

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


Stabilisierung von Eisenoxid-Nanostrukturen mit mehrlagigem Kohlenstoff und Einsatz als Oxidationskatalysator
journal, August 2011


Chemistry of Multitudinous Active Sites for Oxygen Reduction Reaction in Transition Metal–Nitrogen–Carbon Electrocatalysts
journal, November 2015

  • Artyushkova, Kateryna; Serov, Alexey; Rojas-Carbonell, Santiago
  • The Journal of Physical Chemistry C, Vol. 119, Issue 46
  • DOI: 10.1021/acs.jpcc.5b07653

Porphyrin based porous organic polymer as bi-functional catalyst for selective oxidation and Knoevenagel condensation reactions
journal, May 2013


On the deactivation of supported platinum catalysts for selective oxidation of alcohols
journal, March 2014


A Graphene Composite Material with Single Cobalt Active Sites: A Highly Efficient Counter Electrode for Dye-Sensitized Solar Cells
journal, April 2016

  • Cui, Xiaoju; Xiao, Jianping; Wu, Yihui
  • Angewandte Chemie International Edition, Vol. 55, Issue 23
  • DOI: 10.1002/anie.201602097

Stable and catalytically active iron porphyrin-based porous organic polymer: Activity as both a redox and Lewis acid catalyst
journal, July 2015

  • Oveisi, Ali R.; Zhang, Kainan; Khorramabadi-zad, Ahmad
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep10621

Transition metal based catalysts in the aerobic oxidation of alcohols
journal, January 2012

  • Parmeggiani, Camilla; Cardona, Francesca
  • Green Chemistry, Vol. 14, Issue 3
  • DOI: 10.1039/c2gc16344f

Green synthesis of nitriles using non-noble metal oxides-based nanocatalysts
journal, July 2014

  • Jagadeesh, Rajenahally V.; Junge, Henrik; Beller, Matthias
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5123

Nanoscale Fe2O3-Based Catalysts for Selective Hydrogenation of Nitroarenes to Anilines
journal, November 2013


Oxidation of Alcohols with Molecular Oxygen on Solid Catalysts
journal, June 2004

  • Mallat, Tamas; Baiker, Alfons
  • Chemical Reviews, Vol. 104, Issue 6
  • DOI: 10.1021/cr0200116

Recent Advances in Electrocatalysts for Oxygen Reduction Reaction
journal, February 2016


Heterogeneous catalytic properties of unprecedented μ-O-[FeTCPP] 2 dimers (H 2 TCPP = meso-tetra(4-carboxyphenyl)porphyrin): an unusual superhyperfine EPR structure
journal, January 2015

  • Fidalgo-Marijuan, Arkaitz; Barandika, Gotzone; Bazán, Begoña
  • Dalton Transactions, Vol. 44, Issue 1
  • DOI: 10.1039/C4DT02250E

Efficient aerobic oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran on supported Ru catalysts
journal, May 2013


Immobilized metalloporphyrins on 3-aminopropyl-functionalized silica support as heterogeneous catalysts for selective oxidation of primary and secondary alcohols
journal, January 2012

  • Rahimi, Rahmatollah; Ghoreishi, Seyyedeh Zahra; Dekamin, Mohammad G.
  • Monatshefte für Chemie - Chemical Monthly, Vol. 143, Issue 7
  • DOI: 10.1007/s00706-011-0684-2

Perspectives on the kinetics of diol oxidation over supported platinum catalysts in aqueous solution
journal, December 2013


A single iron site confined in a graphene matrix for the catalytic oxidation of benzene at room temperature
journal, December 2015


Highly dispersed iron oxides on mesoporous carbon for selective oxidation of benzyl alcohol with molecular oxygen
journal, January 2014

  • Geng, Longlong; Zhang, Xiuyan; Zhang, Wenxiang
  • Chemical Communications, Vol. 50, Issue 22
  • DOI: 10.1039/c3cc47332e

Synthesis, characterization and catalytic performance of a Fe polyoxometalate/silica composite in the oxidation of alcohols with hydrogen peroxide
journal, October 2014


Selective Oxidation of Alcohols to Esters Using Heterogeneous Co 3 O 4 –N@C Catalysts under Mild Conditions
journal, July 2013

  • Jagadeesh, Rajenahally V.; Junge, Henrik; Pohl, Marga-Martina
  • Journal of the American Chemical Society, Vol. 135, Issue 29
  • DOI: 10.1021/ja403615c

Tuning Catalytic Activity between Homogeneous and Heterogeneous Catalysis: Improved Activity and Selectivity of Free Nano-Fe2O3 in Selective Oxidations
journal, November 2007

  • Shi, Feng; Tse, Man Kin; Pohl, Marga-Matina
  • Angewandte Chemie International Edition, Vol. 46, Issue 46
  • DOI: 10.1002/anie.200703418

Visible-Light-Driven Oxidation of Primary C–H Bonds over CdS with Dual Co-catalysts Graphene and TiO2
journal, November 2013

  • Yang, Min-Quan; Zhang, Yanhui; Zhang, Nan
  • Scientific Reports, Vol. 3, Issue 1
  • DOI: 10.1038/srep03314

Unravelling the Structure of Electrocatalytically Active Fe-N Complexes in Carbon for the Oxygen Reduction Reaction
journal, August 2014

  • Zhu, Yansong; Zhang, Bingsen; Liu, Xin
  • Angewandte Chemie International Edition, Vol. 53, Issue 40
  • DOI: 10.1002/anie.201405314

A noble metal-free proton-exchange membrane fuel cell based on bio-inspired molecular catalysts
journal, January 2015

  • Tran, P. D.; Morozan, A.; Archambault, S.
  • Chemical Science, Vol. 6, Issue 3
  • DOI: 10.1039/C4SC03774J

Mechanism of reductive oxygen adsorption on active carbons with various surface chemistry
journal, January 2004


Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators
journal, June 2016


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


Podlike N-Doped Carbon Nanotubes Encapsulating FeNi Alloy Nanoparticles: High-Performance Counter Electrode Materials for Dye-Sensitized Solar Cells
journal, May 2014

  • Zheng, Xiaojia; Deng, Jiao; Wang, Nan
  • Angewandte Chemie International Edition, Vol. 53, Issue 27
  • DOI: 10.1002/anie.201400388

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

Single-atom dispersed Co–N–C catalyst: structure identification and performance for hydrogenative coupling of nitroarenes
journal, January 2016

  • Liu, Wengang; Zhang, Leilei; Yan, Wensheng
  • Chemical Science, Vol. 7, Issue 9
  • DOI: 10.1039/C6SC02105K

Über die Rolle von Metallen in Elektrokatalysatoren auf Basis von stickstoffdotiertem Kohlenstoff für die Sauerstoffreduktion
journal, July 2015


Co–N–C Catalyst for C–C Coupling Reactions: On the Catalytic Performance and Active Sites
journal, October 2015


Hydrocarbon oxidation by homogeneous and heterogeneous non-heme iron (III) catalysts with H2O2
journal, November 2010


Hydrogenation using iron oxide–based nanocatalysts for the synthesis of amines
journal, March 2015

  • Jagadeesh, Rajenahally V.; Stemmler, Tobias; Surkus, Annette-Enrica
  • Nature Protocols, Vol. 10, Issue 4
  • DOI: 10.1038/nprot.2015.025

Mechanism of Copper(I)/TEMPO-Catalyzed Aerobic Alcohol Oxidation
journal, January 2013

  • Hoover, Jessica M.; Ryland, Bradford L.; Stahl, Shannon S.
  • Journal of the American Chemical Society, Vol. 135, Issue 6
  • DOI: 10.1021/ja3117203

Oxidation of Alcohols with Molecular Oxygen on Solid Catalysts
journal, September 2004


Synthesis and Characterization of Iron–Nitrogen-Doped Graphene/Core–Shell Catalysts: Efficient Oxidative Dehydrogenation of N -Heterocycles
journal, August 2015

  • Cui, Xinjiang; Li, Yuehui; Bachmann, Stephan
  • Journal of the American Chemical Society, Vol. 137, Issue 33
  • DOI: 10.1021/jacs.5b05674

Works referencing / citing this record:

Die facettenreiche Reaktivität heterogener Einzelatom‐Katalysatoren
journal, November 2018

  • Mitchell, Sharon; Vorobyeva, Evgeniya; Pérez‐Ramírez, Javier
  • Angewandte Chemie, Vol. 130, Issue 47
  • DOI: 10.1002/ange.201806936

The Multifaceted Reactivity of Single-Atom Heterogeneous Catalysts
journal, October 2018

  • Mitchell, Sharon; Vorobyeva, Evgeniya; Pérez-Ramírez, Javier
  • Angewandte Chemie International Edition, Vol. 57, Issue 47
  • DOI: 10.1002/anie.201806936

Mono-Atomic Fe Centers in Nitrogen/Carbon Monolayers for Liquid-Phase Selective Oxidation Reaction
journal, July 2018


Single Atom Catalysts on Carbon-Based Materials
journal, November 2018


Recent Advances in Iron Catalyzed Oxidation Reactions of Organic Compounds
journal, August 2017


Promoting effect of solvent on Cu/CoO catalyst for selective glycerol oxidation under alkaline conditions
journal, January 2018

  • Dodekatos, Georgios; Ternieden, Jan; Schünemann, Stefan
  • Catalysis Science & Technology, Vol. 8, Issue 19
  • DOI: 10.1039/c8cy01284a

Metal-free catalytic oxidation of benzylic alcohols for benzaldehyde
journal, January 2019

  • Wang, Zhiyong; Shi, Jie; Wang, Dan
  • Reaction Chemistry & Engineering, Vol. 4, Issue 3
  • DOI: 10.1039/c8re00265g

A robust iron catalyst for the selective hydrogenation of substituted (iso)quinolones
journal, January 2018

  • Sahoo, Basudev; Kreyenschulte, Carsten; Agostini, Giovanni
  • Chemical Science, Vol. 9, Issue 42
  • DOI: 10.1039/c8sc02744g

Single-atom catalysts and their applications in organic chemistry
journal, January 2018

  • Yan, Huan; Su, Chenliang; He, Jun
  • Journal of Materials Chemistry A, Vol. 6, Issue 19
  • DOI: 10.1039/c8ta01940a

Oxidative cleavage of β-O-4 bonds in lignin model compounds with a single-atom Co catalyst
journal, January 2019

  • Liu, Sijie; Bai, Lichen; van Muyden, Antoine P.
  • Green Chemistry, Vol. 21, Issue 8
  • DOI: 10.1039/c9gc00293f

Photochemical oxidation of benzylic primary and secondary alcohols utilizing air as the oxidant
journal, January 2020

  • Nikitas, Nikolaos F.; Tzaras, Dimitrios Ioannis; Triandafillidi, Ierasia
  • Green Chemistry, Vol. 22, Issue 2
  • DOI: 10.1039/c9gc03000j

Single-atom catalyst: a rising star for green synthesis of fine chemicals
journal, August 2018

  • Zhang, Leilei; Ren, Yujing; Liu, Wengang
  • National Science Review, Vol. 5, Issue 5
  • DOI: 10.1093/nsr/nwy077

The Multifaceted Reactivity of Single-Atom Heterogeneous Catalysts
text, January 2018


Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles
journal, April 2018


Selective Catalytic Oxidation of Benzyl Alcohol to Benzaldehyde by Nitrates
journal, March 2020