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

Hallac, Basseem B.; Brown, Jared C.; Stavitski, Eli; Harrison, Roger G.; Argyle, Morris D.

doi:10.3390/catal8020063

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

Journal Article · Sun Feb 04 00:00:00 EST 2018 · Catalysts

DOI:https://doi.org/10.3390/catal8020063· OSTI ID:1438322

Hallac, Basseem B. ^[1]; Brown, Jared C. ^[2]; Stavitski, Eli ^[3]; Harrison, Roger G. ^[4]; ^[4]

Brigham Young Univ., Provo, UT (United States); Phillips 66, Bartlesville, OK (United States)
Brigham Young Univ., Provo, UT (United States); Micron Technology, Boise, ID (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Brigham Young Univ., Provo, UT (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012704

OSTI ID:: 1438322

Report Number(s):: BNL--205683-2018-JAAM

Journal Information:: Catalysts, Journal Name: Catalysts Journal Issue: 2 Vol. 8; ISSN 2073-4344; ISSN CATACJ

Publisher:: MDPICopyright Statement

Country of Publication:: United States

Language:: English

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

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