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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 CH 4 → CH 3OH conversion. This experimental and computational study provides clear evidence that low Ni loadings on a CeO 2(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 CO 2, 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]
  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 Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
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.
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. doi:10.1021/jacs.8b03809.
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. doi:10.1021/jacs.8b03809. https://www.osti.gov/servlets/purl/1440348.
@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 = {2018},
month = {5}
}

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