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

Title: 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.

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

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

Grant/Contract Number:: SC0012704

OSTI ID:: 1438322

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

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

Publisher:: MDPICopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 5 works

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References (38)

The Cu Promoter in an Iron−Chromium−Oxide Based Water−Gas Shift Catalyst under Industrial Conditions Studied by in-Situ XAFS Puig-Molina, Anna; Cano, Fernando Morales; Janssens, Ton V. W. The Journal of Physical Chemistry C, Vol. 114, Issue 36 https://doi.org/10.1021/jp1035103	journal	August 2010
Application of Operando XAS, XRD, and Raman Spectroscopy for Phase Speciation in Water Gas Shift Reaction Catalysts Patlolla, A.; Carino, E. V.; Ehrlich, S. N. ACS Catalysis, Vol. 2, Issue 11 https://doi.org/10.1021/cs300414c	journal	September 2012
Effect of particle size distributions on absorbance spectra of gold nanoparticles Doak, J.; Gupta, R. K.; Manivannan, K. Physica E: Low-dimensional Systems and Nanostructures, Vol. 42, Issue 5 https://doi.org/10.1016/j.physe.2010.01.004	journal	March 2010
Redox Properties of Ruthenium Nitrosyl Porphyrin Complexes with Different Axial Ligation: Structural, Spectroelectrochemical (IR, UV−Visible, and EPR), and Theoretical Studies Singh, Priti; Das, Atanu Kumar; Sarkar, Biprajit Inorganic Chemistry, Vol. 47, Issue 16 https://doi.org/10.1021/ic702371t	journal	August 2008
Reduction characteristics of copper oxide in cerium and zirconium oxide systems Kundakovic, Lj; Flytzani-Stephanopoulos, M. Applied Catalysis A: General, Vol. 171, Issue 1 https://doi.org/10.1016/S0926-860X(98)00056-8	journal	June 1998
Is there a difference between surface and bulk oxidation levels in partially reduced metal oxide catalysts? Evidence from methane oxidative coupling kinetics Labinger, Jay A.; Ott, Kevin C. Catalysis Letters, Vol. 4, Issue 3 https://doi.org/10.1007/BF00765941	journal	January 1990
Kinetics of the water-gas shift reaction over a La0.7Ce0.2FeO3 perovskite-like catalyst using simulated coal-derived syngas at high temperature Hla, San Shwe; Sun, Y.; Duffy, G. J. International Journal of Hydrogen Energy, Vol. 36, Issue 1 https://doi.org/10.1016/j.ijhydene.2010.10.015	journal	January 2011
Radiation Through a Foggy Atmosphere Schuster, Arthur The Astrophysical Journal, Vol. 21 https://doi.org/10.1086/141186	journal	January 1905
Studies of the role of the copper promoter in the iron oxide/chromia high temperature water gas shift catalyst Rhodes, Colin; Hutchings, Graham J. Physical Chemistry Chemical Physics, Vol. 5, Issue 12 https://doi.org/10.1039/b303236c	journal	January 2003
In situ UV−Visible Spectroscopic Measurements of Kinetic Parameters and Active Sites for Catalytic Oxidation of Alkanes on Vanadium Oxides ^† Argyle, Morris D.; Chen, Kaidong; Iglesia, Enrique The Journal of Physical Chemistry B, Vol. 109, Issue 6 https://doi.org/10.1021/jp040166c	journal	February 2005
Photoelectrophoresis of colloidal iron oxides. Part 2.—Magnetite (Fe ₃ O ₄ ) Boxall, Colin; Kelsall, Geoff; Zhang, Zhao J. Chem. Soc., Faraday Trans., Vol. 92, Issue 5 https://doi.org/10.1039/FT9969200791	journal	January 1996
High temperature water gas shift catalysts with alumina Popa, Tiberiu; Xu, Guoqing; Barton, Thomas F. Applied Catalysis A: General, Vol. 379, Issue 1-2 https://doi.org/10.1016/j.apcata.2010.02.021	journal	May 2010
Activity Patterns for the ‘‘Water Gas Shift Reaction Over Supported Precious Metal Catalysts’’ Lei, Yun; Cant, Noel W.; Trimm, David L. Catalysis Letters, Vol. 103, Issue 1-2 https://doi.org/10.1007/s10562-005-6516-4	journal	September 2005
Recent conceptual advances in the catalysis science of mixed metal oxide catalytic materials Wachs, Israel E. Catalysis Today, Vol. 100, Issue 1-2 https://doi.org/10.1016/j.cattod.2004.12.019	journal	February 2005
Promotion of Fe3O4/Cr2O3 high temperature water gas shift catalyst Rhodes, Colin; Peter Williams, B.; King, Frank Catalysis Communications, Vol. 3, Issue 8 https://doi.org/10.1016/S1566-7367(02)00156-5	journal	August 2002
Effects of temperature and wavelength choice on in-situ dissolution test of Cimetidine tablets Li, Xin-Xia; Wang, Yan; Xu, Ping-Ping Journal of Pharmaceutical Analysis, Vol. 3, Issue 1 https://doi.org/10.1016/j.jpha.2012.06.001	journal	February 2013
Microstructural studies of the copper promoted iron oxide/chromia water-gas shift catalyst Edwards, M. A.; Whittle, D. M.; Rhodes, C. Physical Chemistry Chemical Physics, Vol. 4, Issue 15 https://doi.org/10.1039/b202347b	journal	June 2002
Single-crystalline, wormlike hematite photoanodes for efficient solar water splitting Kim, Jae Young; Magesh, Ganesan; Youn, Duck Hyun Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep02681	journal	September 2013
Influence of lanthanum on the performance of Zr-Co/activated carbon catalysts in Fischer-Tropsch synthesis Wang, Tao; Ding, Yunjie; Lü, Yuan Journal of Natural Gas Chemistry, Vol. 17, Issue 2 https://doi.org/10.1016/S1003-9953(08)60043-2	journal	June 2008
Silver species reduction upon exposure of Ag/Al2O3 catalyst to gaseous ethanol: An in situ Quick-XANES study Sayah, Elie; La Fontaine, Camille; Briois, Valérie Catalysis Today, Vol. 189, Issue 1 https://doi.org/10.1016/j.cattod.2012.03.055	journal	July 2012
The oxidation state of iron determined by Fe K-edge XANES—application to iron gall ink in historical manuscripts Wilke, Max; Hahn, Oliver; Woodland, Alan B. Journal of Analytical Atomic Spectrometry, Vol. 24, Issue 10 https://doi.org/10.1039/b904438h	journal	January 2009
UV–visible spectra of perovskite iron-doped Ba0.72Sr0.28TiO3 Zhu, Yudan; Sun, Dazhi; Huang, Qiong Materials Letters, Vol. 62, Issue 3 https://doi.org/10.1016/j.matlet.2007.05.041	journal	February 2008
Iron-based catalysts for the water—gas shift reaction promoted by first-row transition metal oxides Andreev, A.; Idakiev, V.; Mihajlova, D. Applied Catalysis, Vol. 22, Issue 2 https://doi.org/10.1016/S0166-9834(00)82645-7	journal	April 1986
Effect of temperature and reduction on the activity of high temperature water gas shift catalysts Gonzalez, J. C.; Gonzalez, M. G.; Laborde, M. A. Applied Catalysis, Vol. 20, Issue 1-2 https://doi.org/10.1016/0166-9834(86)80005-7	journal	January 1986
The role of vanadium on the properties of iron based catalysts for the water gas shift reaction Júnior, Ivan Lima; Millet, Jean-Marc M.; Aouine, Mimoun Applied Catalysis A: General, Vol. 283, Issue 1-2 https://doi.org/10.1016/j.apcata.2004.12.038	journal	April 2005
A kinetic study on the structural and functional roles of lanthana in iron-based high temperature water–gas shift catalysts Hallac, Basseem B.; Brown, Jared C.; Baxter, Larry L. International Journal of Hydrogen Energy, Vol. 39, Issue 14 https://doi.org/10.1016/j.ijhydene.2014.02.170	journal	May 2014
XANES Spectroscopy: A Promising Tool for Toxicology: Gunter, Karlene K.; Miller, Lisa M.; Aschner, Michael NeuroToxicology, Vol. 23, Issue 2 https://doi.org/10.1016/S0161-813X(02)00034-7	journal	July 2002
Dynamics of redox behavior of nano-sized VOx species over Ti–Si-MCM-41 from time-resolved in situ UV/Vis analysis Ovsitser, Olga; Cherian, Maymol; Brückner, Angelika Journal of Catalysis, Vol. 265, Issue 1 https://doi.org/10.1016/j.jcat.2009.04.005	journal	July 2009
Effect of Ce on the structural features and catalytic properties of La(0.9−x)CexFeO3 perovskite-like catalysts for the high temperature water–gas shift reaction Sun, Y.; Hla, S. S.; Duffy, G. J. International Journal of Hydrogen Energy, Vol. 36, Issue 1 https://doi.org/10.1016/j.ijhydene.2010.09.093	journal	January 2011
In Situ UV–vis–NIR Diffuse Reflectance and Raman Spectroscopic Studies of Propane Oxidation over ZrO2-Supported Vanadium Oxide Catalysts Gao, Xingtao; Jehng, Jih-Mirn; Wachs, Israel E. Journal of Catalysis, Vol. 209, Issue 1 https://doi.org/10.1006/jcat.2002.3635	journal	July 2002
The electronic structures of Fe3+ coordination sites in iron oxides: Applications to spectra, bonding, and magnetism Sherman, David M. Physics and Chemistry of Minerals, Vol. 12, Issue 3 https://doi.org/10.1007/BF00308210	journal	July 1985
Quaternary Ammonium Oxidative Demethylation: X-ray Crystallographic, Resonance Raman, and UV–Visible Spectroscopic Analysis of a Rieske-Type Demethylase Daughtry, Kelly D.; Xiao, Youli; Stoner-Ma, Deborah Journal of the American Chemical Society, Vol. 134, Issue 5 https://doi.org/10.1021/ja2111898	journal	January 2012
Quantitative analysis in diffuse reflectance spectrometry: A modified Kubelka-Munk equation Christy, Alfred A.; Kvalheim, Olav M.; Velapoldi, Rance A. Vibrational Spectroscopy, Vol. 9, Issue 1 https://doi.org/10.1016/0924-2031(94)00065-O	journal	May 1995
In situ UV–Vis diffuse reflectance spectroscopy — on line activity measurements of supported chromium oxide catalysts: relating isobutane dehydrogenation activity with Cr-speciation via experimental design Weckhuysen, Bert M.; Verberckmoes, An A.; Debaere, Jan Journal of Molecular Catalysis A: Chemical, Vol. 151, Issue 1-2 https://doi.org/10.1016/S1381-1169(99)00259-9	journal	February 2000
In situ UV-visible assessment of extent of reduction during oxidation reactions on oxide catalysts Argyle, Morris D.; Chen, Kaidong; Resini, Carlo Chemical Communications, Issue 16 https://doi.org/10.1039/b305264h	journal	January 2003
Reactive behaviors of iron-based shift catalyst promoted by ceria Hu, Yanping; Jin, Hengfang; Liu, Jinrong Chemical Engineering Journal, Vol. 78, Issue 2-3 https://doi.org/10.1016/S1385-8947(00)00133-9	journal	August 2000
Electronic structures of iron(III) and manganese(IV) (hydr)oxide minerals: Thermodynamics of photochemical reductive dissolution in aquatic environments Sherman, David M. Geochimica et Cosmochimica Acta, Vol. 69, Issue 13 https://doi.org/10.1016/j.gca.2005.01.023	journal	July 2005
Recent Conceptual Advances in the Catalysis Science of Mixed Metal Oxide Catalytic Materials Wachs, Israel E. ChemInform, Vol. 36, Issue 30 https://doi.org/10.1002/chin.200530211	journal	July 2005

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36 MATERIALS SCIENCE
iron water gas shift catalysts
extent of reduction
UV-visible spectroscopy
XANES

Title: 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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