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Title: In Situ UV-Visible Assessment of Iron-Based High-Temperature Water-Gas Shift Catalysts Promoted with Lanthana: An Extent of Reduction Study

Abstract

Here, the extent of reduction of unsupported iron-based high-temperature water-gas shift catalysts with small (<5 wt %) lanthana contents was studied using UV-visible spectroscopy. Temperature- programmed reduction measurements showed that lanthana content higher than 0.5 wt % increased the extent of reduction to metallic Fe, while 0.5 wt % of lanthana facilitated the reduction to Fe3O4. In situ measurements on the iron oxide catalysts using mass and UV-visible spectroscopies permitted the quantification of the extent of reduction under temperature-programmed reduction and high-temperature water-gas shift conditions. The oxidation states were successfully calibrated against normalized absorbance spectra of visible light using the Kubelka-Munk theory. The normalized absorbance relative to the fully oxidized Fe2O3 increased as the extent of reduction increased. XANES suggested that the average bulk iron oxidation state during the water-gas shift reaction was Fe+2.57 for the catalyst with no lanthana and Fe+2.54 for the catalysts with 1 wt % lanthana. However, the UV-vis spectra suggest that the surface oxidation state of iron would be Fe+2.31 for the catalyst with 1 wt % lanthana if the oxidation state of iron in the catalyst with 0 wt % lanthana were Fe+2.57. The findings of this paper emphasize the importance of surface sensitivemore » UV-visible spectroscopy for determining the extent of catalyst reduction during operation. Furthermore, the paper highlights the potential to use bench-scale UV-visible spectroscopy to study the surface chemistry of catalysts instead of less-available synchrotron X-ray radiation facilities.« less

Authors:
 [1];  [2];  [3];  [4]; ORCiD logo [4]
  1. Brigham Young Univ., Provo, UT (United States); Phillips 66, Bartlesville, OK (United States)
  2. Brigham Young Univ., Provo, UT (United States); Micron Technology, Boise, ID (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Brigham Young Univ., Provo, UT (United States)
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:
1438322
Report Number(s):
BNL-205683-2018-JAAM
Journal ID: ISSN 2073-4344; CATACJ
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Catalysts
Additional Journal Information:
Journal Volume: 8; Journal Issue: 2; Journal ID: ISSN 2073-4344
Publisher:
MDPI
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; iron water gas shift catalysts; extent of reduction; UV-visible spectroscopy; XANES

Citation Formats

Hallac, Basseem B., Brown, Jared C., Stavitski, Eli, Harrison, Roger G., and Argyle, Morris D. In Situ UV-Visible Assessment of Iron-Based High-Temperature Water-Gas Shift Catalysts Promoted with Lanthana: An Extent of Reduction Study. United States: N. p., 2018. Web. doi:10.3390/catal8020063.
Hallac, Basseem B., Brown, Jared C., Stavitski, Eli, Harrison, Roger G., & Argyle, Morris D. In Situ UV-Visible Assessment of Iron-Based High-Temperature Water-Gas Shift Catalysts Promoted with Lanthana: An Extent of Reduction Study. United States. doi:10.3390/catal8020063.
Hallac, Basseem B., Brown, Jared C., Stavitski, Eli, Harrison, Roger G., and Argyle, Morris D. Sun . "In Situ UV-Visible Assessment of Iron-Based High-Temperature Water-Gas Shift Catalysts Promoted with Lanthana: An Extent of Reduction Study". United States. doi:10.3390/catal8020063. https://www.osti.gov/servlets/purl/1438322.
@article{osti_1438322,
title = {In Situ UV-Visible Assessment of Iron-Based High-Temperature Water-Gas Shift Catalysts Promoted with Lanthana: An Extent of Reduction Study},
author = {Hallac, Basseem B. and Brown, Jared C. and Stavitski, Eli and Harrison, Roger G. and Argyle, Morris D.},
abstractNote = {Here, the extent of reduction of unsupported iron-based high-temperature water-gas shift catalysts with small (<5 wt %) lanthana contents was studied using UV-visible spectroscopy. Temperature- programmed reduction measurements showed that lanthana content higher than 0.5 wt % increased the extent of reduction to metallic Fe, while 0.5 wt % of lanthana facilitated the reduction to Fe3O4. In situ measurements on the iron oxide catalysts using mass and UV-visible spectroscopies permitted the quantification of the extent of reduction under temperature-programmed reduction and high-temperature water-gas shift conditions. The oxidation states were successfully calibrated against normalized absorbance spectra of visible light using the Kubelka-Munk theory. The normalized absorbance relative to the fully oxidized Fe2O3 increased as the extent of reduction increased. XANES suggested that the average bulk iron oxidation state during the water-gas shift reaction was Fe+2.57 for the catalyst with no lanthana and Fe+2.54 for the catalysts with 1 wt % lanthana. However, the UV-vis spectra suggest that the surface oxidation state of iron would be Fe+2.31 for the catalyst with 1 wt % lanthana if the oxidation state of iron in the catalyst with 0 wt % lanthana were Fe+2.57. The findings of this paper emphasize the importance of surface sensitive UV-visible spectroscopy for determining the extent of catalyst reduction during operation. Furthermore, the paper highlights the potential to use bench-scale UV-visible spectroscopy to study the surface chemistry of catalysts instead of less-available synchrotron X-ray radiation facilities.},
doi = {10.3390/catal8020063},
journal = {Catalysts},
number = 2,
volume = 8,
place = {United States},
year = {2018},
month = {2}
}

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