Understanding complete oxidation of methane on spinel oxides at a molecular level
Abstract
It is crucial to develop a catalyst made of earth-abundant elements highly active for a complete oxidation of methane at a relatively low temperature. NiCo2O4 consisting of earth-abundant elements which can completely oxidize methane in the temperature range of 350-550 °C. Being a cost-effective catalyst, NiCo2O4 exhibits activity higher than precious-metal-based catalysts. Here we report that the higher catalytic activity at the relatively low temperature results from the integration of nickel cations, cobalt cations and surface lattice oxygen atoms/oxygen vacancies at the atomic scale. Finally, in situ studies of complete oxidation of methane on NiCo2O4 and theoretical simulations show that methane dissociates to methyl on nickel cations and then couple with surface lattice oxygen atoms to form -CH3O with a following dehydrogenation to -CH2O; a following oxidative dehydrogenation forms CHO; CHO is transformed to product molecules through two different sub-pathways including dehydrogenation of OCHO and CO oxidation.
- Authors:
-
- Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemical and Petroleum Engineering; Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemistry
- Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemical and Petroleum Engineering; Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemistry
- Queens Univ., Blefast (United Kingdom). School of Chemistry and Chemical Engineering
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
- 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 Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1319196
- Grant/Contract Number:
- AC05-00OR22725; FG02-12ER16353
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Communications
- Additional Journal Information:
- Journal Volume: 6; Journal ID: ISSN 2041-1723
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE
Citation Formats
Tao, Franklin Feng, Shan, Jun-jun, Nguyen, Luan, Wang, Ziyun, Zhang, Shiran, Zhang, Li, Wu, Zili, Huang, Weixin, Zeng, Shibi, and Hu, P. Understanding complete oxidation of methane on spinel oxides at a molecular level. United States: N. p., 2015.
Web. doi:10.1038/ncomms8798.
Tao, Franklin Feng, Shan, Jun-jun, Nguyen, Luan, Wang, Ziyun, Zhang, Shiran, Zhang, Li, Wu, Zili, Huang, Weixin, Zeng, Shibi, & Hu, P. Understanding complete oxidation of methane on spinel oxides at a molecular level. United States. https://doi.org/10.1038/ncomms8798
Tao, Franklin Feng, Shan, Jun-jun, Nguyen, Luan, Wang, Ziyun, Zhang, Shiran, Zhang, Li, Wu, Zili, Huang, Weixin, Zeng, Shibi, and Hu, P. Tue .
"Understanding complete oxidation of methane on spinel oxides at a molecular level". United States. https://doi.org/10.1038/ncomms8798. https://www.osti.gov/servlets/purl/1319196.
@article{osti_1319196,
title = {Understanding complete oxidation of methane on spinel oxides at a molecular level},
author = {Tao, Franklin Feng and Shan, Jun-jun and Nguyen, Luan and Wang, Ziyun and Zhang, Shiran and Zhang, Li and Wu, Zili and Huang, Weixin and Zeng, Shibi and Hu, P.},
abstractNote = {It is crucial to develop a catalyst made of earth-abundant elements highly active for a complete oxidation of methane at a relatively low temperature. NiCo2O4 consisting of earth-abundant elements which can completely oxidize methane in the temperature range of 350-550 °C. Being a cost-effective catalyst, NiCo2O4 exhibits activity higher than precious-metal-based catalysts. Here we report that the higher catalytic activity at the relatively low temperature results from the integration of nickel cations, cobalt cations and surface lattice oxygen atoms/oxygen vacancies at the atomic scale. Finally, in situ studies of complete oxidation of methane on NiCo2O4 and theoretical simulations show that methane dissociates to methyl on nickel cations and then couple with surface lattice oxygen atoms to form -CH3O with a following dehydrogenation to -CH2O; a following oxidative dehydrogenation forms CHO; CHO is transformed to product molecules through two different sub-pathways including dehydrogenation of OCHO and CO oxidation.},
doi = {10.1038/ncomms8798},
journal = {Nature Communications},
number = ,
volume = 6,
place = {United States},
year = {Tue Aug 04 00:00:00 EDT 2015},
month = {Tue Aug 04 00:00:00 EDT 2015}
}
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Works referenced in this record:
Reverse microemulsion synthesis of nanostructured complex oxides for catalytic combustion
journal, January 2000
- Zarur, Andrey J.; Ying, Jackie Y.
- Nature, Vol. 403, Issue 6765
Exceptional Activity for Methane Combustion over Modular Pd@CeO2 Subunits on Functionalized Al2O3
journal, August 2012
- Cargnello, M.; Jaen, J. J. D.; Garrido, J. C. H.
- Science, Vol. 337, Issue 6095
Low-Temperature Oxidation of Methane
journal, August 2012
- Farrauto, R. J.
- Science, Vol. 337, Issue 6095
Catalyst screening using a stone DTA apparatus I. Oxidation of toluene over cobalt-metal-oxide catalysts
journal, January 1973
- Papadatos, K.
- Journal of Catalysis, Vol. 28, Issue 1
Oxidation of propene on mixed oxides of copper and cobalt
journal, January 1979
- Baussart, H.; Delobel, R.; Le Bras, M.
- Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 75, Issue 0
Complete oxidation of methane at low temperature over noble metal based catalysts: a review
journal, November 2002
- Gélin, Patrick; Primet, Michel
- Applied Catalysis B: Environmental, Vol. 39, Issue 1, p. 1-37
Complete oxidation of methane at low temperature over Pt and Pd catalysts for the abatement of lean-burn natural gas fuelled vehicles emissions: influence of water and sulphur containing compounds
journal, August 2003
- Gélin, Patrick; Urfels, Laetitia; Primet, Michel
- Catalysis Today, Vol. 83, Issue 1-4
Structural Characteristics of Natural-Gas-Vehicle-Aged Oxidation Catalyst
journal, April 2013
- Honkanen, Mari; Kärkkäinen, Marja; Viitanen, Ville
- Topics in Catalysis, Vol. 56, Issue 9-10
Palladium catalyst performance for methane emissions abatement from lean burn natural gas vehicles
journal, December 1997
- Lampert, J.; Kazi, M.; Farrauto, R.
- Applied Catalysis B: Environmental, Vol. 14, Issue 3-4
Consequences of Metal–Oxide Interconversion for C–H Bond Activation during CH 4 Reactions on Pd Catalysts
journal, October 2013
- Chin, Ya-Huei (Cathy); Buda, Corneliu; Neurock, Matthew
- Journal of the American Chemical Society, Vol. 135, Issue 41
WGS Catalysis and In Situ Studies of CoO 1– x , PtCo n /Co 3 O 4 , and Pt m Co m ′ /CoO 1– x Nanorod Catalysts
journal, May 2013
- Zhang, Shiran; Shan, Jun-jun; Zhu, Yuan
- Journal of the American Chemical Society, Vol. 135, Issue 22
The role of low-coordinate oxygen on Co 3 O 4 (110) in catalyticCO oxidation
journal, January 2011
- Jiang, De-en; Dai, Sheng
- Phys. Chem. Chem. Phys., Vol. 13, Issue 3
Low-temperature oxidation of CO catalysed by Co3O4 nanorods
journal, April 2009
- Xie, Xiaowei; Li, Yong; Liu, Zhi-Quan
- Nature, Vol. 458, Issue 7239, p. 746-749
Catalysis and In Situ Studies of Rh 1 /Co 3 O 4 Nanorods in Reduction of NO with H 2
journal, April 2013
- Wang, Lei; Zhang, Shiran; Zhu, Yuan
- ACS Catalysis, Vol. 3, Issue 5
Design of an in-house ambient pressure AP-XPS using a bench-top X-ray source and the surface chemistry of ceria under reaction conditions
journal, January 2012
- Tao, Franklin (Feng)
- Chemical Communications, Vol. 48, Issue 32
A comparative study of the thermal stability of nickel, copper and zinc spinel cobaltites
journal, October 1991
- Klissurski, D. G.; Uzunova, E. L.
- Thermochimica Acta, Vol. 189, Issue 1
Reaction-Driven Restructuring of Rh-Pd and Pt-Pd Core-Shell Nanoparticles
journal, November 2008
- Tao, F.; Grass, M. E.; Zhang, Y.
- Science, Vol. 322, Issue 5903
Restructuring Transition Metal Oxide Nanorods for 100% Selectivity in Reduction of Nitric Oxide with Carbon Monoxide
journal, June 2013
- Zhang, Shiran; Shan, Junjun; Zhu, Yuan
- Nano Letters, Vol. 13, Issue 7
Atomistic Simulation of Orientation Dependence in Shock-Induced Initiation of Pentaerythritol Tetranitrate
journal, January 2013
- Shan, Tzu-Ray; Wixom, Ryan R.; Mattsson, Ann E.
- The Journal of Physical Chemistry B, Vol. 117, Issue 3
Importance of the Metal-Oxide Interface in Catalysis: In Situ Studies of the Water-Gas Shift Reaction by Ambient-Pressure X-ray Photoelectron Spectroscopy
journal, April 2013
- Mudiyanselage, Kumudu; Senanayake, Sanjaya D.; Feria, Leticia
- Angewandte Chemie International Edition, Vol. 52, Issue 19
Reactivity Differences of Nanocrystals and Continuous Films of α-Fe 2 O 3 on Au(111) Studied with In Situ X-ray Photoelectron Spectroscopy
journal, December 2010
- Deng, Xingyi; Lee, Junseok; Wang, Congjun
- The Journal of Physical Chemistry C, Vol. 114, Issue 51
Surface Chemistry of Cu in the Presence of CO 2 and H 2 O
journal, September 2008
- Deng, Xingyi; Verdaguer, Albert; Herranz, Tirma
- Langmuir, Vol. 24, Issue 17
Progress in Solid Oxide Fuel Cells with Nickel-Based Anodes Operating on Methane and Related Fuels
journal, July 2013
- Wang, Wei; Su, Chao; Wu, Yuzhou
- Chemical Reviews, Vol. 113, Issue 10
Origin of extraordinarily high catalytic activity of Co3O4 and its morphological chemistry for CO oxidation at low temperature
journal, December 2012
- Wang, Hai-Feng; Kavanagh, Richard; Guo, Yang-Long
- Journal of Catalysis, Vol. 296
Activity and coke formation of nickel and nickel carbide in dry reforming: A deactivation scheme from density functional theory
journal, March 2014
- Wang, Ziyun; Cao, X. -M.; Zhu, Jinghao
- Journal of Catalysis, Vol. 311
Methane transformation to carbon and hydrogen on Pd(100): Pathways and energetics from density functional theory calculations
journal, January 2002
- Zhang, C. J.; Hu, P.
- The Journal of Chemical Physics, Vol. 116, Issue 1
Mechanistic Studies of Hydrocarbon Combustion and Synthesis on Noble Metals
journal, June 2008
- Inderwildi, Oliver R.; Jenkins, Stephen J.; King, David A.
- Angewandte Chemie International Edition, Vol. 47, Issue 28
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998
- Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
- Physical Review B, Vol. 57, Issue 3, p. 1505-1509
Break-Up of Stepped Platinum Catalyst Surfaces by High CO Coverage
journal, February 2010
- Tao, F.; Dag, S.; Wang, L. -W.
- Science, Vol. 327, Issue 5967
In Situ Studies of Chemistry and Structure of Materials in Reactive Environments
journal, January 2011
- Tao, F.; Salmeron, M.
- Science, Vol. 331, Issue 6014
In-Situ Studies of Nanocatalysis
journal, April 2013
- Zhang, Shiran; Nguyen, Luan; Zhu, Yuan
- Accounts of Chemical Research, Vol. 46, Issue 8
In Situ Surface Chemistries and Catalytic Performances of Ceria Doped with Palladium, Platinum, and Rhodium in Methane Partial Oxidation for the Production of Syngas
journal, October 2013
- Zhu, Yuan; Zhang, Shiran; Shan, Jun-jun
- ACS Catalysis, Vol. 3, Issue 11
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 49, Issue 20, p. 14251-14269
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
A DFT study of methanol oxidation on Co3O4
journal, February 2014
- Lv, Cun-Qin; Liu, Chang; Wang, Gui-Chang
- Catalysis Communications, Vol. 45
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Identification of General Linear Relationships between Activation Energies and Enthalpy Changes for Dissociation Reactions at Surfaces
journal, April 2003
- Michaelides, Angelos; Liu, Z. -P.; Zhang, C. J.
- Journal of the American Chemical Society, Vol. 125, Issue 13
General Rules for Predicting Where a Catalytic Reaction Should Occur on Metal Surfaces: A Density Functional Theory Study of C−H and C−O Bond Breaking/Making on Flat, Stepped, and Kinked Metal Surfaces
journal, February 2003
- Liu, Zhi-Pan; Hu, P.
- Journal of the American Chemical Society, Vol. 125, Issue 7, p. 1958-1967
CO Oxidation on Pt(111): An Ab Initio Density Functional Theory Study
journal, April 1998
- Alavi, Ali; Hu, Peijun; Deutsch, Thierry
- Physical Review Letters, Vol. 80, Issue 16
Works referencing / citing this record:
Bowtie-Shaped NiCo 2 O 4 Catalysts for Low-Temperature Methane Combustion
journal, January 2019
- Dai, Yiling; Kumar, Vanama Pavan; Zhu, Chujie
- Advanced Functional Materials, Vol. 29, Issue 8
Design of active NiCo 2 O 4‐δ spinel catalyst for abatement of CO‐CH 4 emissions from CNG fueled vehicles
journal, April 2018
- Trivedi, S.; Prasad, R.; Gautam, S. K.
- AIChE Journal, Vol. 64, Issue 7
Ferrocene‐Linkage‐Facilitated Charge Separation in Conjugated Microporous Polymers
journal, February 2019
- Ma, Li; Liu, Yilin; Liu, Yi
- Angewandte Chemie, Vol. 131, Issue 13
Low-Temperature Transformation of Methane to Methanol on Pd 1 O 4 Single Sites Anchored on the Internal Surface of Microporous Silicate
journal, September 2016
- Huang, Weixin; Zhang, Shiran; Tang, Yu
- Angewandte Chemie International Edition, Vol. 55, Issue 43
Ferrocene-Linkage-Facilitated Charge Separation in Conjugated Microporous Polymers
journal, February 2019
- Ma, Li; Liu, Yilin; Liu, Yi
- Angewandte Chemie International Edition, Vol. 58, Issue 13
Photoionization Mass Spectrometry for Online Detection of Reactive and Unstable Gas‐Phase Intermediates in Heterogeneous Catalytic Reactions
journal, December 2019
- You, Rui; Huang, Weixin
- ChemCatChem, Vol. 12, Issue 3
Catalytic Oxidation of Methane: Pd and Beyond: Catalytic Oxidation of Methane: Pd and Beyond
journal, June 2018
- Monai, Matteo; Montini, Tiziano; Gorte, Raymond J.
- European Journal of Inorganic Chemistry, Vol. 2018, Issue 25
Deactivation Mechanism, Countermeasures, and Enhanced CH 4 Oxidation Performance of Nickel/Cobalt Oxides
journal, September 2019
- Chen, Junfei; Zou, Xuelin; Rui, Zebao
- Energy Technology, Vol. 8, Issue 8
Perovskite catalysts for methane combustion: applications, design, effects for reactivity and partial oxidation
journal, August 2019
- Bashan, Veysi; Ust, Yasin
- International Journal of Energy Research
Photocatalytic oxidation of methane over silver decorated zinc oxide nanocatalysts
journal, July 2016
- Chen, Xuxing; Li, Yunpeng; Pan, Xiaoyang
- Nature Communications, Vol. 7, Issue 1
Catalysis on singly dispersed bimetallic sites
journal, August 2015
- Zhang, Shiran; Nguyen, Luan; Liang, Jin-Xia
- Nature Communications, Vol. 6, Issue 1
Stable complete methane oxidation over palladium based zeolite catalysts
journal, June 2018
- Petrov, Andrey W.; Ferri, Davide; Krumeich, Frank
- Nature Communications, Vol. 9, Issue 1
Operando chemistry of catalyst surfaces during catalysis
journal, January 2017
- Dou, Jian; Sun, Zaicheng; Opalade, Adedamola A.
- Chemical Society Reviews, Vol. 46, Issue 7
Transition of surface phase of cobalt oxide during CO oxidation
journal, January 2018
- Tang, Yu; Ma, Lingjuan; Dou, Jian
- Physical Chemistry Chemical Physics, Vol. 20, Issue 9
Interactions of gaseous molecules with X-ray photons and photoelectrons in AP-XPS study of solid surface in gas phase
journal, January 2018
- Tao, Franklin (Feng); Nguyen, Luan
- Physical Chemistry Chemical Physics, Vol. 20, Issue 15
Synthesis of K–Pd doped NiCo 2 O 4−δ by reactive calcination route for oxidation of CO–CH 4 emissions from CNG vehicles
journal, January 2018
- Trivedi, S.; Prasad, R.
- New Journal of Chemistry, Vol. 42, Issue 6
Facile fabrication of shape-controlled Co x Mn y O β nanocatalysts for benzene oxidation at low temperatures
journal, January 2018
- Wang, Xiuyun; Zhao, Weitao; Zhang, Tianhua
- Chemical Communications, Vol. 54, Issue 17
Evidence of the O–Pd–O and Pd–O 4 structure units as oxide seeds and their origin on Pd(211): revealing the mechanism of surface oxide formation
journal, January 2019
- Cheng, Xiran; Wang, Ziyun; Mao, Yu
- Physical Chemistry Chemical Physics, Vol. 21, Issue 12
Selectively anchoring Pt single atoms at hetero-interfaces of γ-Al 2 O 3 /NiS to promote the hydrogen evolution reaction
journal, January 2018
- Feng, Yangyang; Guan, Yongxin; Zhang, Huijuan
- Journal of Materials Chemistry A, Vol. 6, Issue 25
Stable complete methane oxidation over palladium based zeolite catalysts
text, January 2018
- W., Petrov, Andrey; Davide, Ferri,; Frank, Krumeich,
- ETH Zurich
Ultrahigh Electrocatalytic Conversion of Methane at Room Temperature
journal, September 2017
- Ma, Ming; Jin, Bing Jun; Li, Ping
- Advanced Science, Vol. 4, Issue 12
Synthesis of a Highly Stable Pd@CeO 2 Catalyst for Methane Combustion with the Synergistic Effect of Urea and Citric Acid
journal, December 2018
- Cai, Guohui; Luo, Wei; Xiao, Yihong
- ACS Omega, Vol. 3, Issue 12
Photocatalytic oxidation of methane over silver decorated zinc oxide nanocatalysts
journal, July 2016
- Chen, Xuxing; Li, Yunpeng; Pan, Xiaoyang
- Nature Communications, Vol. 7, Issue 1
Stable complete methane oxidation over palladium based zeolite catalysts
text, January 2018
- W., Petrov, Andrey; Davide, Ferri,; Frank, Krumeich,
- ETH Zurich