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Title: Conversion of Methane into Methanol and Ethanol over Nickel Oxide on Ceria-Zirconia Catalysts in a Single Reactor

Abstract

Direct conversion of methane into alcohols is a promising technology for converting stranded methane reserves into liquids that can be transported in pipelines and upgraded to value-added chemicals. We demonstrate that a catalyst consisting of small nickel oxide clusters supported on ceria-zirconia (NiO/CZ) can selectively oxidize methane to methanol and ethanol in a single, steady-state process at 723 K using O2 as an abundantly available oxidant. The presence of steam is required to obtain alcohols rather than CO2 as the product of catalytic combustion. The unusual activity of this catalyst is attributed to the synergy between the small Lewis acidic NiO clusters and the redox-active CZ support, which also stabilizes the small NiO clusters.

Authors:
 [1];  [1];  [1];  [2];  [3];  [3];  [4]; ORCiD logo [1]
  1. School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW Atlanta GA 30332 USA
  2. National Renewable Energy Laboratory, Golden CO 80401 USA
  3. Environmental Molecular Sciences Laboratory, Pacific Northwest National Lab, Richland WA 99354 USA
  4. National Synchrotron Light Source II, Brookhaven National Laboratory, Upton NY 11973 USA
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1406736
Report Number(s):
PNNL-SA-123257
Journal ID: ISSN 1433-7851; 48308; KP1704020
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Volume: 56; Journal Issue: 44; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Okolie, Chukwuemeka, Belhseine, Yasmeen F., Lyu, Yimeng, Yung, Matthew M., Engelhard, Mark H., Kovarik, Libor, Stavitski, Eli, and Sievers, Carsten. Conversion of Methane into Methanol and Ethanol over Nickel Oxide on Ceria-Zirconia Catalysts in a Single Reactor. United States: N. p., 2017. Web. doi:10.1002/anie.201704704.
Okolie, Chukwuemeka, Belhseine, Yasmeen F., Lyu, Yimeng, Yung, Matthew M., Engelhard, Mark H., Kovarik, Libor, Stavitski, Eli, & Sievers, Carsten. Conversion of Methane into Methanol and Ethanol over Nickel Oxide on Ceria-Zirconia Catalysts in a Single Reactor. United States. doi:10.1002/anie.201704704.
Okolie, Chukwuemeka, Belhseine, Yasmeen F., Lyu, Yimeng, Yung, Matthew M., Engelhard, Mark H., Kovarik, Libor, Stavitski, Eli, and Sievers, Carsten. Tue . "Conversion of Methane into Methanol and Ethanol over Nickel Oxide on Ceria-Zirconia Catalysts in a Single Reactor". United States. doi:10.1002/anie.201704704.
@article{osti_1406736,
title = {Conversion of Methane into Methanol and Ethanol over Nickel Oxide on Ceria-Zirconia Catalysts in a Single Reactor},
author = {Okolie, Chukwuemeka and Belhseine, Yasmeen F. and Lyu, Yimeng and Yung, Matthew M. and Engelhard, Mark H. and Kovarik, Libor and Stavitski, Eli and Sievers, Carsten},
abstractNote = {Direct conversion of methane into alcohols is a promising technology for converting stranded methane reserves into liquids that can be transported in pipelines and upgraded to value-added chemicals. We demonstrate that a catalyst consisting of small nickel oxide clusters supported on ceria-zirconia (NiO/CZ) can selectively oxidize methane to methanol and ethanol in a single, steady-state process at 723 K using O2 as an abundantly available oxidant. The presence of steam is required to obtain alcohols rather than CO2 as the product of catalytic combustion. The unusual activity of this catalyst is attributed to the synergy between the small Lewis acidic NiO clusters and the redox-active CZ support, which also stabilizes the small NiO clusters.},
doi = {10.1002/anie.201704704},
journal = {Angewandte Chemie (International Edition)},
issn = {1433-7851},
number = 44,
volume = 56,
place = {United States},
year = {2017},
month = {9}
}

Works referenced in this record:

Selective Oxidation of Methane by the Bis(μ-oxo)dicopper Core Stabilized on ZSM-5 and Mordenite Zeolites
journal, February 2005

  • Groothaert, Marijke H.; Smeets, Pieter J.; Sels, Bert F.
  • Journal of the American Chemical Society, Vol. 127, Issue 5
  • DOI: 10.1021/ja047158u

Oxidative Methane Upgrading
journal, July 2012


Rationalization of the Catalytic Behavior of Lanthanide Oxides and Praseodymium Molybdates in Total and Selective Oxidation of Isobutene
journal, December 2001

  • De Smet, Frédéric; Ruiz, Patricio; Delmon, Bernard
  • The Journal of Physical Chemistry B, Vol. 105, Issue 49
  • DOI: 10.1021/jp0124600

Platinum Catalysts for the High-Yield Oxidation of Methane to a Methanol Derivative
journal, April 1998


Direct catalytic conversion of methane to acetic acid in an aqueous medium
journal, April 1994


Mechanistic Studies on the Hydroxylation of Methane by Methane Monooxygenase
journal, June 2003

  • Baik, Mu-Hyun; Newcomb, Martin; Friesner, Richard A.
  • Chemical Reviews, Vol. 103, Issue 6
  • DOI: 10.1021/cr950244f

Catalytic Oxidation of Methane into Methanol over Copper-Exchanged Zeolites with Oxygen at Low Temperature
journal, April 2016


Oxidation of methane to methanol on the surface of FeZSM-5 zeolite
journal, April 2013


Kinetics of hydrogen activation on ceria–zirconia
journal, September 2015


Status and prospects in higher alcohols synthesis from syngas
journal, January 2017

  • Luk, Ho Ting; Mondelli, Cecilia; Ferré, Daniel Curulla
  • Chemical Society Reviews, Vol. 46, Issue 5
  • DOI: 10.1039/C6CS00324A

A [Cu 2 O] 2+ core in Cu-ZSM-5, the active site in the oxidation of methane to methanol
journal, October 2009

  • Woertink, Julia S.; Smeets, Pieter J.; Groothaert, Marijke H.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 45
  • DOI: 10.1073/pnas.0910461106

Hydrogen production by catalytic cracking of methane over nickel gauze under periodic reactor operation
journal, January 2001


A Spectroscopic Characterization of the Reduction of Ceria from Electronic Transitions of Intrinsic Point Defects
journal, June 1994

  • Binet, Claude; Badri, Ahmed; Lavalley, Jean-Claude
  • The Journal of Physical Chemistry, Vol. 98, Issue 25
  • DOI: 10.1021/j100076a025

Catalytic and spectroscopic studies of Ag1.2V3CeyO8+x catalysts for oxidation of toluene
journal, October 1991


Hydrodeoxygenation of Guaiacol over Ceria-Zirconia Catalysts
journal, June 2015

  • Schimming, Sarah M.; LaMont, Onaje D.; König, Michael
  • ChemSusChem, Vol. 8, Issue 12
  • DOI: 10.1002/cssc.201500317

Iron complexes in zeolites as a new model of methane monooxygenase
journal, July 1997

  • Panov, G. I.; Sobolev, V. I.; Dubkov, K. A.
  • Reaction Kinetics and Catalysis Letters, Vol. 61, Issue 2
  • DOI: 10.1007/BF02478380

Mixed alcohols synthesis from syngas over Cs- and Ni-modified Cu/CeO2 catalysts
journal, February 2013


Direct Catalytic Conversion of Methane to Methanol in an Aqueous Medium by using Copper-Promoted Fe-ZSM-5
journal, April 2012

  • Hammond, Ceri; Forde, Michael M.; Ab Rahim, Mohd Hasbi
  • Angewandte Chemie International Edition, Vol. 51, Issue 21
  • DOI: 10.1002/anie.201108706

Water-gas shift: in situ spectroscopic studies of noble metal promoted ceria catalysts for CO removal in fuel cell reformers and mechanistic implications
journal, May 2004


C−H Bond Activation and Organometallic Intermediates on Isolated Metal Centers on Oxide Surfaces
journal, February 2010


Direct conversion of methane to methanol
journal, September 1997


Heterolytic Splitting of H 2 and CH 4 on γ-Alumina as a Structural Probe for Defect Sites
journal, November 2006

  • Joubert, Jérôme; Salameh, Alain; Krakoviack, Vincent
  • The Journal of Physical Chemistry B, Vol. 110, Issue 47
  • DOI: 10.1021/jp0641841

Bio-inspired oxidation of methane in water catalyzed by N-bridged diiron phthalocyanine complex
journal, January 2008

  • Sorokin, Alexander B.; Kudrik, Evgeny V.; Bouchu, Denis
  • Chemical Communications, Issue 22
  • DOI: 10.1039/b804405h

Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol
journal, June 2015

  • Grundner, Sebastian; Markovits, Monica A. C.; Li, Guanna
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8546

Active Nonmetallic Au and Pt Species on Ceria-Based Water-Gas Shift Catalysts
journal, August 2003


Direct Catalytic Conversion of Methane to Methanol in an Aqueous Medium by using Copper-Promoted Fe-ZSM-5
journal, April 2012

  • Hammond, Ceri; Forde, Michael M.; Ab Rahim, Mohd Hasbi
  • Angewandte Chemie, Vol. 124, Issue 21
  • DOI: 10.1002/ange.201108706

Advances in low temperature Fischer-Tropsch synthesis
journal, January 1995


Diiron N-bridged species bearing phthalocyanine ligand catalyzes oxidation of methane, propane and benzene under mild conditions
journal, October 2008

  • Kudrik, Evgeny V.; Afanasiev, Pavel; Bouchu, Denis
  • Journal of Porphyrins and Phthalocyanines, Vol. 12, Issue 10
  • DOI: 10.1142/S1088424608000431

Identification of molybdenum oxide nanostructures on zeolites for natural gas conversion
journal, April 2015


Direct, Nonoxidative Conversion of Methane to Ethylene, Aromatics, and Hydrogen
journal, May 2014


Pre-reforming of natural gas on a Ni catalyst
journal, March 2005


Oxidation of methane by a biological dicopper centre
journal, April 2010

  • Balasubramanian, Ramakrishnan; Smith, Stephen M.; Rawat, Swati
  • Nature, Vol. 465, Issue 7294
  • DOI: 10.1038/nature08992

Selective oxidation of methane to synthesis gas using transition metal catalysts
journal, March 1990

  • Ashcroft, A. T.; Cheetham, A. K.; Foord, J. S.
  • Nature, Vol. 344, Issue 6264
  • DOI: 10.1038/344319a0

Conversion of methane to methanol on copper-containing small-pore zeolites and zeotypes
journal, January 2015

  • Wulfers, M. J.; Teketel, S.; Ipek, B.
  • Chemical Communications, Vol. 51, Issue 21
  • DOI: 10.1039/C4CC09645B

Generation of active oxygen species on solid surfaces. Opportunity for novel oxidation technologies over zeolites
journal, June 1998


Synthesis of Ethanol via Syngas on Cu/SiO 2 Catalysts with Balanced Cu 0 –Cu + Sites
journal, May 2012

  • Gong, Jinlong; Yue, Hairong; Zhao, Yujun
  • Journal of the American Chemical Society, Vol. 134, Issue 34
  • DOI: 10.1021/ja3034153

Infrared Study of Oxygen Adsorption and Activation on Cerium–Zirconium Mixed Oxides
journal, November 2000


    Works referencing / citing this record:

    Experimental and theoretical study of multinuclear indium–oxo clusters in CHA zeolite for CH 4 activation at room temperature
    journal, January 2019

    • Maeno, Zen; Yasumura, Shunsaku; Liu, Chong
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 25
    • DOI: 10.1039/c9cp01873e

    Experimental and theoretical study of multinuclear indium–oxo clusters in CHA zeolite for CH 4 activation at room temperature
    journal, January 2019

    • Maeno, Zen; Yasumura, Shunsaku; Liu, Chong
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 25
    • DOI: 10.1039/c9cp01873e