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Title: Direct Conversion of Methane to Methanol on Ni-Ceria Surfaces: Metal-Support Interactions and Water-enabled Catalytic Conversion by Site Blocking

Abstract

The transformation of methane into methanol or higher alcohols at moderate temperature and pressure conditions is of great environmental interest and remains a challenge despite many efforts. Extended surfaces of metallic nickel are inactive for a direct CH4 → CH3OH conversion. This experimental and computational study provides clear evidence that low Ni loadings on a CeO2(111) support can perform a direct catalytic cycle for the generation of methanol at low temperature using oxygen and water as reactants, with a higher selectivity than ever reported for ceria-based catalysts. On the basis of ambient pressure X-ray photoemission spectroscopy and density functional theory calculations, we demonstrate that water plays a crucial role in blocking catalyst sites where methyl species could fully decompose, an essential factor for diminishing the production of CO and CO2, and in generating sites on which methoxy species and ultimately methanol can form. In addition to water-site blocking, one needs the effects of metal-support interactions to bind and activate methane and water. Lastly, these findings should be considered when designing metal/oxide catalysts for converting methane to value-added chemicals and fuels.

Authors:
 [1];  [2];  [3];  [4];  [5];  [2];  [3];  [5];  [6];  [2]; ORCiD logo [2]
+ Show Author Affiliations
  1. Instituto de Fisica Rosario (IFIR), Santa Fe (Argentina)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Univ. Central de Venezuela, Caracas (Venezuela)
  4. Science and Technology Facilities Council (STFC), Harwell Campus, Oxford (United Kingdom). Diamond Light Source, Ltd.
  5. Charles Univ., Prague (Czech Republic)
  6. Instituto de Catalisis y Petroleoquimica, Madrid (Spain)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1440348
Report Number(s):
BNL-205725-2018-JAAM
Journal ID: ISSN 0002-7863
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 24; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Lustemberg, Pablo G., Palomino, Robert M., Gutierrez, Ramon A., Grinter, David C., Vorokhta, Mykhailo, Liu, Zongyuan, Ramirez, Pedro J., Matolin, Vladimir, Ganduglia-Pirovano, M. Veronica, Senanayake, Sanjaya D., and Rodriguez, Jose A. Direct Conversion of Methane to Methanol on Ni-Ceria Surfaces: Metal-Support Interactions and Water-enabled Catalytic Conversion by Site Blocking. United States: N. p., 2018. Web. doi:10.1021/jacs.8b03809.
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Lustemberg, Pablo G., Palomino, Robert M., Gutierrez, Ramon A., Grinter, David C., Vorokhta, Mykhailo, Liu, Zongyuan, Ramirez, Pedro J., Matolin, Vladimir, Ganduglia-Pirovano, M. Veronica, Senanayake, Sanjaya D., & Rodriguez, Jose A. Direct Conversion of Methane to Methanol on Ni-Ceria Surfaces: Metal-Support Interactions and Water-enabled Catalytic Conversion by Site Blocking. United States. https://doi.org/10.1021/jacs.8b03809
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Lustemberg, Pablo G., Palomino, Robert M., Gutierrez, Ramon A., Grinter, David C., Vorokhta, Mykhailo, Liu, Zongyuan, Ramirez, Pedro J., Matolin, Vladimir, Ganduglia-Pirovano, M. Veronica, Senanayake, Sanjaya D., and Rodriguez, Jose A. Mon . "Direct Conversion of Methane to Methanol on Ni-Ceria Surfaces: Metal-Support Interactions and Water-enabled Catalytic Conversion by Site Blocking". United States. https://doi.org/10.1021/jacs.8b03809. https://www.osti.gov/servlets/purl/1440348.
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@article{osti_1440348,
title = {Direct Conversion of Methane to Methanol on Ni-Ceria Surfaces: Metal-Support Interactions and Water-enabled Catalytic Conversion by Site Blocking},
author = {Lustemberg, Pablo G. and Palomino, Robert M. and Gutierrez, Ramon A. and Grinter, David C. and Vorokhta, Mykhailo and Liu, Zongyuan and Ramirez, Pedro J. and Matolin, Vladimir and Ganduglia-Pirovano, M. Veronica and Senanayake, Sanjaya D. and Rodriguez, Jose A.},
abstractNote = {The transformation of methane into methanol or higher alcohols at moderate temperature and pressure conditions is of great environmental interest and remains a challenge despite many efforts. Extended surfaces of metallic nickel are inactive for a direct CH4 → CH3OH conversion. This experimental and computational study provides clear evidence that low Ni loadings on a CeO2(111) support can perform a direct catalytic cycle for the generation of methanol at low temperature using oxygen and water as reactants, with a higher selectivity than ever reported for ceria-based catalysts. On the basis of ambient pressure X-ray photoemission spectroscopy and density functional theory calculations, we demonstrate that water plays a crucial role in blocking catalyst sites where methyl species could fully decompose, an essential factor for diminishing the production of CO and CO2, and in generating sites on which methoxy species and ultimately methanol can form. In addition to water-site blocking, one needs the effects of metal-support interactions to bind and activate methane and water. Lastly, these findings should be considered when designing metal/oxide catalysts for converting methane to value-added chemicals and fuels.},
doi = {10.1021/jacs.8b03809},
journal = {Journal of the American Chemical Society},
number = 24,
volume = 140,
place = {United States},
year = {Mon May 28 00:00:00 EDT 2018},
month = {Mon May 28 00:00:00 EDT 2018}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1021/jacs.8b03809
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Cited by: 98 works
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Figures / Tables:

Figure 1 Figure 1: C 1s XPS Spectra collected after exposing Ni(111), bottom panel, CeO2(111) and Ni/CeO2(111), top panel, to 1 Torr of methane at 300 K for 5 minutes. To generate the H2O/Ni(111) and H2O/Ni/CeO2(111) samples, the corresponding surfaces were exposed to 1 Torr of water at 300 K before dosingmore » methane.« less
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    Works referencing / citing this record:

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    • Silva, Telles Cardoso; dos Santos Pires, Maíra; de Castro, Alexandre Alves
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    Controlling the Reduction Extent for Metal Catalysts
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    Structure and bonding in NbX5 X = (F, Cl, Br and I) complexes: a molecular orbital perspective in the C–H bond activation
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    Selective oxidation of methane to methanol with H 2 O 2 over an Fe-MFI zeolite catalyst using sulfolane solvent
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    • Xiao, Peipei; Wang, Yong; Nishitoba, Toshiki
    • Chemical Communications, Vol. 55, Issue 20
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    A Supported Nickel Catalyst Stabilized by a Surface Digging Effect for Efficient Methane Oxidation
    journal, November 2019

    • Zhou, Huang; Liu, Tianyang; Zhao, Xuyan
    • Angewandte Chemie International Edition, Vol. 58, Issue 51
    • DOI: 10.1002/anie.201912785

    Tuning the Structure of Pt Nanoparticles through Support Interactions: An in Situ Polarized X-ray Absorption Study Coupled with Atomistic Simulations
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