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Title: In Situ Characterization of Mesoporous Co/CeO2 Catalysts for the High-Temperature Water-Gas Shift

Abstract

Here, mesoporous Co/CeO2 catalysts were found to exhibit significant activity for the high-temperature water-gas shift (WGS) reaction with cobalt loadings as low as 1 wt %. The catalysts feature a uniform dispersion of cobalt within the CeO2 fluorite type lattice with no evidence of discrete cobalt phase segregation. In situ XANES and ambient pressure XPS experiments were used to elucidate the active state of the catalysts as partially reduced cerium oxide doped with oxidized cobalt atoms. In situ XRD and DRIFTS experiments suggest facile cerium reduction and oxygen vacancy formation, particularly with lower cobalt loadings. In situ DRIFTS analysis also revealed the presence of surface carbonate and bidentate formate species under reaction conditions, which may be associated with additional mechanistic pathways for the WGS reaction. Deactivation behavior was observed with higher cobalt loadings. XANES data suggest the formation of small metallic cobalt clusters at temperatures above 400 °C may be responsible. Notably, this deactivation was not observed for the 1% cobalt loaded catalyst, which exhibited the highest activity per unit of cobalt.

Authors:
ORCiD logo [1];  [2];  [2]; ORCiD logo [3];  [1]; ORCiD logo [4];  [5]; ORCiD logo [4];  [5]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [4]
  1. Stony Brook Univ., Stony Brook, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Univ. of Connecticut, Storrs, CT (United States)
  3. Technical Univ. of California, Barcelona (Spain)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States)
  5. Stony Brook Univ., Stony Brook, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Univ. of Connecticut, Storrs, CT (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1454818
Alternate Identifier(s):
OSTI ID: 1597857
Report Number(s):
BNL-205763-2018-JAAM
Journal ID: ISSN 1932-7447
Grant/Contract Number:  
SC0012704; FG02-86ER13622
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 16; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Vovchok, Dimitriy, Guild, Curtis J., Dissanayake, Shanka, Llorca, Jordi, Stavitski, Eli, Liu, Zongyuan, Palomino, Robert M., Waluyo, Iradwikanari, Li, Yuanyuan, Frenkel, Anatoly I., Rodriguez, Jose A., Suib, Steven L., and Senanayake, Sanjaya D. In Situ Characterization of Mesoporous Co/CeO2 Catalysts for the High-Temperature Water-Gas Shift. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.8b01271.
Vovchok, Dimitriy, Guild, Curtis J., Dissanayake, Shanka, Llorca, Jordi, Stavitski, Eli, Liu, Zongyuan, Palomino, Robert M., Waluyo, Iradwikanari, Li, Yuanyuan, Frenkel, Anatoly I., Rodriguez, Jose A., Suib, Steven L., & Senanayake, Sanjaya D. In Situ Characterization of Mesoporous Co/CeO2 Catalysts for the High-Temperature Water-Gas Shift. United States. https://doi.org/10.1021/acs.jpcc.8b01271
Vovchok, Dimitriy, Guild, Curtis J., Dissanayake, Shanka, Llorca, Jordi, Stavitski, Eli, Liu, Zongyuan, Palomino, Robert M., Waluyo, Iradwikanari, Li, Yuanyuan, Frenkel, Anatoly I., Rodriguez, Jose A., Suib, Steven L., and Senanayake, Sanjaya D. Wed . "In Situ Characterization of Mesoporous Co/CeO2 Catalysts for the High-Temperature Water-Gas Shift". United States. https://doi.org/10.1021/acs.jpcc.8b01271. https://www.osti.gov/servlets/purl/1454818.
@article{osti_1454818,
title = {In Situ Characterization of Mesoporous Co/CeO2 Catalysts for the High-Temperature Water-Gas Shift},
author = {Vovchok, Dimitriy and Guild, Curtis J. and Dissanayake, Shanka and Llorca, Jordi and Stavitski, Eli and Liu, Zongyuan and Palomino, Robert M. and Waluyo, Iradwikanari and Li, Yuanyuan and Frenkel, Anatoly I. and Rodriguez, Jose A. and Suib, Steven L. and Senanayake, Sanjaya D.},
abstractNote = {Here, mesoporous Co/CeO2 catalysts were found to exhibit significant activity for the high-temperature water-gas shift (WGS) reaction with cobalt loadings as low as 1 wt %. The catalysts feature a uniform dispersion of cobalt within the CeO2 fluorite type lattice with no evidence of discrete cobalt phase segregation. In situ XANES and ambient pressure XPS experiments were used to elucidate the active state of the catalysts as partially reduced cerium oxide doped with oxidized cobalt atoms. In situ XRD and DRIFTS experiments suggest facile cerium reduction and oxygen vacancy formation, particularly with lower cobalt loadings. In situ DRIFTS analysis also revealed the presence of surface carbonate and bidentate formate species under reaction conditions, which may be associated with additional mechanistic pathways for the WGS reaction. Deactivation behavior was observed with higher cobalt loadings. XANES data suggest the formation of small metallic cobalt clusters at temperatures above 400 °C may be responsible. Notably, this deactivation was not observed for the 1% cobalt loaded catalyst, which exhibited the highest activity per unit of cobalt.},
doi = {10.1021/acs.jpcc.8b01271},
journal = {Journal of Physical Chemistry. C},
number = 16,
volume = 122,
place = {United States},
year = {2018},
month = {4}
}

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