Conversion of Methane to Methanol and Ethanol over Nickel Oxide on Ceria-Zirconia Catalysts in a Single Reactor
Abstract
Abstract The conversion of methane into alcohols under moderate reaction conditions 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 convert methane to methanol and ethanol in a single, steady‐state process at 723 K using O 2 as an abundantly available oxidant. The presence of steam is required to obtain alcohols rather than CO 2 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:
-
- Georgia Inst. of Technology, Atlanta, GA (United States)
- National Renewable Energy Lab. (NREL), Golden, CO (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- National Renewable Energy Laboratory (NREL), Golden, CO (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1395093
- Alternate Identifier(s):
- OSTI ID: 1394849
- Report Number(s):
- NREL/JA-5100-69074
Journal ID: ISSN 1433-7851
- Grant/Contract Number:
- AC36-08GO28308; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 44; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; C-H activation; heterogeneous catalysis; Lewis acid; methane; nickel
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 to 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 to Methanol and Ethanol over Nickel Oxide on Ceria-Zirconia Catalysts in a Single Reactor. United States. https://doi.org/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 to Methanol and Ethanol over Nickel Oxide on Ceria-Zirconia Catalysts in a Single Reactor". United States. https://doi.org/10.1002/anie.201704704. https://www.osti.gov/servlets/purl/1395093.
@article{osti_1395093,
title = {Conversion of Methane to 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 = {Abstract The conversion of methane into alcohols under moderate reaction conditions 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 convert methane to methanol and ethanol in a single, steady‐state process at 723 K using O 2 as an abundantly available oxidant. The presence of steam is required to obtain alcohols rather than CO 2 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)},
number = 44,
volume = 56,
place = {United States},
year = {Tue Aug 08 00:00:00 EDT 2017},
month = {Tue Aug 08 00:00:00 EDT 2017}
}
Web of Science
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
Oxidative Methane Upgrading
journal, July 2012
- Hammond, Ceri; Conrad, Sabrina; Hermans, Ive
- ChemSusChem, Vol. 5, Issue 9
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
Platinum Catalysts for the High-Yield Oxidation of Methane to a Methanol Derivative
journal, April 1998
- Periana, R. A.
- Science, Vol. 280, Issue 5363
Direct catalytic conversion of methane to acetic acid in an aqueous medium
journal, April 1994
- Lin, Minren; Sen, Ayusman
- Nature, Vol. 368, Issue 6472
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
Catalytic Oxidation of Methane into Methanol over Copper-Exchanged Zeolites with Oxygen at Low Temperature
journal, April 2016
- Narsimhan, Karthik; Iyoki, Kenta; Dinh, Kimberly
- ACS Central Science, Vol. 2, Issue 6
Oxidation of methane to methanol on the surface of FeZSM-5 zeolite
journal, April 2013
- Starokon, Eugeny V.; Parfenov, Mikhail V.; Arzumanov, Sergey S.
- Journal of Catalysis, Vol. 300
Kinetics of hydrogen activation on ceria–zirconia
journal, September 2015
- Schimming, Sarah M.; Foo, Guo Shiou; LaMont, Onaje D.
- Journal of Catalysis, Vol. 329
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
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
Hydrogen production by catalytic cracking of methane over nickel gauze under periodic reactor operation
journal, January 2001
- Monnerat, B.; Kiwi-Minsker, L.; Renken, A.
- Chemical Engineering Science, Vol. 56, Issue 2
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
Catalytic and spectroscopic studies of Ag1.2V3CeyO8+x catalysts for oxidation of toluene
journal, October 1991
- Yan, Z.
- Journal of Catalysis, Vol. 131, Issue 2
Hydrodeoxygenation of Guaiacol over Ceria-Zirconia Catalysts
journal, June 2015
- Schimming, Sarah M.; LaMont, Onaje D.; König, Michael
- ChemSusChem, Vol. 8, Issue 12
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
Mixed alcohols synthesis from syngas over Cs- and Ni-modified Cu/CeO2 catalysts
journal, February 2013
- Liu, Yanyong; Murata, Kazuhisa; Inaba, Megumu
- Fuel, Vol. 104
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
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
- Jacobs, Gary; Patterson, Patricia M.; Williams, Leann
- Applied Catalysis A: General, Vol. 262, Issue 2
C−H Bond Activation and Organometallic Intermediates on Isolated Metal Centers on Oxide Surfaces
journal, February 2010
- Coperet, Christophe
- Chemical Reviews, Vol. 110, Issue 2
Direct conversion of methane to methanol
journal, September 1997
- Raja, Robert; Ratnasamy, Paul
- Applied Catalysis A: General, Vol. 158, Issue 1-2
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
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
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
Active Nonmetallic Au and Pt Species on Ceria-Based Water-Gas Shift Catalysts
journal, August 2003
- Fu, Q.
- Science, Vol. 301, Issue 5635
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
Advances in low temperature Fischer-Tropsch synthesis
journal, January 1995
- Jager, B.; Espinoza, R.
- Catalysis Today, Vol. 23, Issue 1
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
Identification of molybdenum oxide nanostructures on zeolites for natural gas conversion
journal, April 2015
- Gao, J.; Zheng, Y.; Jehng, J. -M.
- Science, Vol. 348, Issue 6235
Direct, Nonoxidative Conversion of Methane to Ethylene, Aromatics, and Hydrogen
journal, May 2014
- Guo, X.; Fang, G.; Li, G.
- Science, Vol. 344, Issue 6184
Pre-reforming of natural gas on a Ni catalyst
journal, March 2005
- Sperle, Thomas; Chen, De; Lødeng, Rune
- Applied Catalysis A: General, Vol. 282, Issue 1-2
Oxidation of methane by a biological dicopper centre
journal, April 2010
- Balasubramanian, Ramakrishnan; Smith, Stephen M.; Rawat, Swati
- Nature, Vol. 465, Issue 7294
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
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
Generation of active oxygen species on solid surfaces. Opportunity for novel oxidation technologies over zeolites
journal, June 1998
- Panov, Gennady I.; Uriarte, Anthony K.; Rodkin, Mikhail A.
- Catalysis Today, Vol. 41, Issue 4
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
Infrared Study of Oxygen Adsorption and Activation on Cerium–Zirconium Mixed Oxides
journal, November 2000
- Descorme, C.; Madier, Y.; Duprez, D.
- Journal of Catalysis, Vol. 196, Issue 1
Hydrogen and synthesis gas by steam- and C02 reforming
journal, January 2002
- Rostrup-Nielsen, Jens R.; Sehested, Jens; Nørskov, Jens K.
- Advances in Catalysis, Vol. 47, p. 65-139
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
Coupling of Methane to Ethane, Ethylene, and Aromatics over Nickel on Ceria-Zirconia at Low Temperatures
journal, May 2018
- Okolie, Chukwuemeka; Lyu, Yimeng; Kovarik, Libor
- ChemCatChem, Vol. 10, Issue 12
Quasicatalytic and catalytic selective oxidation of methane to methanol over solid materials: a review on the roles of water
journal, October 2019
- Shi, Yayun; Liu, Shizhong; Liu, Yiming
- Catalysis Reviews
Nickel Oxide Nano-Particles on 3D Nickel Foam Substrate as a Non-Enzymatic Glucose Sensor
journal, January 2019
- Hayat, Asif; Mane, Sunil Kumar Baburao; Shaishta, Naghma
- Journal of The Electrochemical Society, Vol. 166, Issue 15
Thermodynamic Limitations of the Catalyst Design Space for Methanol Production from Methane
journal, October 2018
- Jocz, Jennifer N.; Medford, Andrew J.; Sievers, Carsten
- ChemCatChem, Vol. 11, Issue 1
Reversible Segregation of Ni in LaFe 0.8 Ni 0.2 O 3± δ During Coke Removal
journal, August 2018
- Steiger, Patrick; Nachtegaal, Maarten; Kröcher, Oliver
- ChemCatChem, Vol. 10, Issue 19
Interfacial CoO x Layers on TiO 2 as an Efficient Catalyst for Solvent-Free Aerobic Oxidation of Hydrocarbons
journal, October 2018
- Wang, Hai; Wang, Liang; Zhang, Jian
- ChemSusChem, Vol. 11, Issue 22