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

Dimitriy Vovchok; Curtis J. Guild; Shanka Dissanayake; Jordi Llorca; Eli Stavitski; Zongyuan Liu; Robert M. Palomino; Iradwikanari Waluyo; Yuanyuan Li; Anatoly I. Frenkel; José A. Rodriguez; Steven L. Suib; Sanjaya D. Senanayake

doi:10.1021/acs.jpcc.8b01271

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

Dimitriy Vovchok, Curtis J. Guild, Shanka Dissanayake, Jordi Llorca, Eli Stavitski, Zongyuan Liu, Robert M. Palomino, Iradwikanari Waluyo, Yuanyuan Li, Anatoly I. Frenkel, José A. Rodriguez, Steven L. Suib, Sanjaya D. Senanayake

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Abstract

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.

Original language	English
Pages (from-to)	8998-9008
Number of pages	11
Journal	Journal of Physical Chemistry C
Volume	122
Issue number	16
DOIs	https://doi.org/10.1021/acs.jpcc.8b01271
State	Published - Apr 26 2018
Externally published	Yes

Funding

The research carried out at Brookhaven National Laboratory was supported by the U.S. Department of Energy, Office of Science and Office of Basic Energy Sciences under Contract No. DE-SC0012704. S.D.S is also supported by a U.S. Department of Energy Early Career Award. This research used resources of the 8-ID (ISS) and 23-ID-2 (IOS) beamlines of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. This work also used resources of the Advanced Photon Source (17B-M), a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. J.L. is a Serra Hunter Fellow and is grateful to the ICREA Academia Program and MINECO/FEDER Grant ENE2015-63969-R and GC 2017 SGR 128. S.L.S. acknowledges support from the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical, Biological and Geological Sciences (Grant DE-FG02-86ER13622A00) as well as the assistance of the Bioscience Electron Microscopy Laboratory of the University of Connecticut and Grant # 1126100 for the purchase of the FEI NovaSEM. A.I.F. acknowledges support from the U.S. Department of Energy, Office of Basic Energy Sciences Division of Chemical, Biological and Geological Sciences (Grant DE-FG02-03ER15476). The authors also acknowledge Dr. Taejin Kim and Mr. Xiaojun Chan from Stony Brook University for making available their infrared spectroscopy facilities for the purposes of this work. The research carried out at Brookhaven National Laboratory was supported by the U.S. Department of Energy, Office of Science and Office of Basic Energy Sciences under Contract No. DE-SC0012704. S.D.S is also supported by a U.S. Department of Energy Early Career Award. This research used resources of the 8-ID (ISS) and 23-ID-2 (IOS) beamlines of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. This work also used resources of the Advanced Photon Source (17B-M), a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. J.L. is a Serra Hunter Fellow and is grateful to the ICREA Academia Program and MINECO/FEDER Grant ENE2015-63969-R and GC 2017 SGR 128. S.L.S. acknowledges support from the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical, Biological and Geological Sciences (Grant DE-FG02-86ER13622A00) as well as the assistance of the Bioscience Electron Microscopy Laboratory of the University of Connecticut and Grant # 1126100 for the purchase of the FEI NovaSEM.

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Vovchok, D., Guild, C. J., Dissanayake, S., Llorca, J., Stavitski, E., Liu, Z., Palomino, R. M., Waluyo, I., Li, Y., Frenkel, A. I., Rodriguez, J. A., Suib, S. L., & Senanayake, S. D. (2018). In Situ Characterization of Mesoporous Co/CeO₂ Catalysts for the High-Temperature Water-Gas Shift. Journal of Physical Chemistry C, 122(16), 8998-9008. https://doi.org/10.1021/acs.jpcc.8b01271

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title = "In Situ Characterization of Mesoporous Co/CeO2 Catalysts for the High-Temperature Water-Gas Shift",

abstract = "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.",

author = "Dimitriy Vovchok and Guild, {Curtis J.} and Shanka Dissanayake and Jordi Llorca and Eli Stavitski and Zongyuan Liu and Palomino, {Robert M.} and Iradwikanari Waluyo and Yuanyuan Li and Frenkel, {Anatoly I.} and Rodriguez, {Jos{\'e} A.} and Suib, {Steven L.} and Senanayake, {Sanjaya D.}",

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doi = "10.1021/acs.jpcc.8b01271",

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Vovchok, D, Guild, CJ, Dissanayake, S, Llorca, J, Stavitski, E, Liu, Z, Palomino, RM, Waluyo, I, Li, Y, Frenkel, AI, Rodriguez, JA, Suib, SL & Senanayake, SD 2018, 'In Situ Characterization of Mesoporous Co/CeO₂ Catalysts for the High-Temperature Water-Gas Shift', Journal of Physical Chemistry C, vol. 122, no. 16, pp. 8998-9008. https://doi.org/10.1021/acs.jpcc.8b01271

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T1 - In Situ Characterization of Mesoporous Co/CeO2 Catalysts for the High-Temperature Water-Gas Shift

AU - Vovchok, Dimitriy

AU - Guild, Curtis J.

AU - Dissanayake, Shanka

AU - Llorca, Jordi

AU - Stavitski, Eli

AU - Liu, Zongyuan

AU - Palomino, Robert M.

AU - Waluyo, Iradwikanari

AU - Li, Yuanyuan

AU - Frenkel, Anatoly I.

AU - Rodriguez, José A.

AU - Suib, Steven L.

AU - Senanayake, Sanjaya D.

PY - 2018/4/26

Y1 - 2018/4/26

N2 - 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.

AB - 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.

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ER -

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

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