Structural investigations of La0.6Sr0.4FeO3-δ under reducing conditions: kinetic and thermodynamic limitations for phase transformations and iron exsolution phenomena
Abstract
The crystal structure changes and iron exsolution behavior of a series of oxygen-deficient lanthanum strontium ferrite (La0.6Sr0.4FeO3-δ, LSF) samples under various inert and reducing conditions up to a maximum temperature of 873 K have been investigated to understand the role of oxygen and iron deficiencies in both processes. Iron exsolution occurs in reductive environments at higher temperatures, leading to the formation of Fe rods or particles at the surface. Utilizing multiple ex situ and in situ methods (in situ X-ray diffraction (XRD), in situ thermogravimetric analysis (TGA), and scanning X-ray absorption near-edge spectroscopy (XANES)), the thermodynamic and kinetic limitations are accordingly assessed. Prior to the iron exsolution, the perovskite undergoes a nonlinear shift of the diffraction peaks to smaller 2θ angles, which can be attributed to a rhombohedral-to-cubic (R$$\overline{3}$$c to Pm$$\overline{3}$$m) structural transition. In reducing atmospheres, the cubic structure is stabilized upon cooling to room temperature, whereas the transition is suppressed under oxidizing conditions. This suggests that an accumulation of oxygen vacancies in the lattice stabilize the cubic phase. The exsolution itself is shown to exhibit a diffusion-limited Avrami-like behavior, where the transport of iron to the Fe-depleted surface-near region is the rate-limiting step.
- Authors:
-
[1];
[2];
[2];
[3];
[1]
- University of Innsbruck (Austria)
- Technical University Berlin (Germany)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Nagoya University, Furo-cho, Chikusa-ku (Japan)
- RIKEN SPring-8 Center, Sayo (Japan)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1485071
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- RSC Advances
- Additional Journal Information:
- Journal Volume: 8; Journal Issue: 6; Journal ID: ISSN 2046-2069
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Götsch, Thomas, Schlicker, Lukas, Bekheet, Maged F., Doran, Andrew, Grünbacher, Matthias, Praty, Corsin, Tada, Mizuki, Matsui, Hirosuke, Ishiguro, Nozomu, Gurlo, Aleksander, Klötzer, Bernhard, and Penner, Simon. Structural investigations of La0.6Sr0.4FeO3-δ under reducing conditions: kinetic and thermodynamic limitations for phase transformations and iron exsolution phenomena. United States: N. p., 2018.
Web. doi:10.1039/c7ra12309d.
Götsch, Thomas, Schlicker, Lukas, Bekheet, Maged F., Doran, Andrew, Grünbacher, Matthias, Praty, Corsin, Tada, Mizuki, Matsui, Hirosuke, Ishiguro, Nozomu, Gurlo, Aleksander, Klötzer, Bernhard, & Penner, Simon. Structural investigations of La0.6Sr0.4FeO3-δ under reducing conditions: kinetic and thermodynamic limitations for phase transformations and iron exsolution phenomena. United States. https://doi.org/10.1039/c7ra12309d
Götsch, Thomas, Schlicker, Lukas, Bekheet, Maged F., Doran, Andrew, Grünbacher, Matthias, Praty, Corsin, Tada, Mizuki, Matsui, Hirosuke, Ishiguro, Nozomu, Gurlo, Aleksander, Klötzer, Bernhard, and Penner, Simon. Mon .
"Structural investigations of La0.6Sr0.4FeO3-δ under reducing conditions: kinetic and thermodynamic limitations for phase transformations and iron exsolution phenomena". United States. https://doi.org/10.1039/c7ra12309d. https://www.osti.gov/servlets/purl/1485071.
@article{osti_1485071,
title = {Structural investigations of La0.6Sr0.4FeO3-δ under reducing conditions: kinetic and thermodynamic limitations for phase transformations and iron exsolution phenomena},
author = {Götsch, Thomas and Schlicker, Lukas and Bekheet, Maged F. and Doran, Andrew and Grünbacher, Matthias and Praty, Corsin and Tada, Mizuki and Matsui, Hirosuke and Ishiguro, Nozomu and Gurlo, Aleksander and Klötzer, Bernhard and Penner, Simon},
abstractNote = {The crystal structure changes and iron exsolution behavior of a series of oxygen-deficient lanthanum strontium ferrite (La0.6Sr0.4FeO3-δ, LSF) samples under various inert and reducing conditions up to a maximum temperature of 873 K have been investigated to understand the role of oxygen and iron deficiencies in both processes. Iron exsolution occurs in reductive environments at higher temperatures, leading to the formation of Fe rods or particles at the surface. Utilizing multiple ex situ and in situ methods (in situ X-ray diffraction (XRD), in situ thermogravimetric analysis (TGA), and scanning X-ray absorption near-edge spectroscopy (XANES)), the thermodynamic and kinetic limitations are accordingly assessed. Prior to the iron exsolution, the perovskite undergoes a nonlinear shift of the diffraction peaks to smaller 2θ angles, which can be attributed to a rhombohedral-to-cubic (R$\overline{3}$c to Pm$\overline{3}$m) structural transition. In reducing atmospheres, the cubic structure is stabilized upon cooling to room temperature, whereas the transition is suppressed under oxidizing conditions. This suggests that an accumulation of oxygen vacancies in the lattice stabilize the cubic phase. The exsolution itself is shown to exhibit a diffusion-limited Avrami-like behavior, where the transport of iron to the Fe-depleted surface-near region is the rate-limiting step.},
doi = {10.1039/c7ra12309d},
journal = {RSC Advances},
number = 6,
volume = 8,
place = {United States},
year = {Mon Jan 15 00:00:00 EST 2018},
month = {Mon Jan 15 00:00:00 EST 2018}
}
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Works referenced in this record:
Anisotropic and Nonlinear Thermal and Chemical Expansion of La 1– x Sr x FeO 3−δ ( x = 0.3, 0.4, 0.5) Perovskite Materials
journal, August 2013
- Chen, Xinzhi; Grande, Tor
- Chemistry of Materials, Vol. 25, Issue 16
Effective ionic radii in oxides and fluorides
journal, May 1969
- Shannon, R. D.; Prewitt, C. T.
- Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 25, Issue 5
Kinetics and mechanisms of exsolution
journal, January 1970
- Yund, Richard A.; McCallister, Robert H.
- Chemical Geology, Vol. 6
Investigation of In-doped BaFeO 3−δ perovskite-type oxygen permeable membranes
journal, January 2015
- Lu, Yao; Zhao, Hailei; Cheng, Xing
- Journal of Materials Chemistry A, Vol. 3, Issue 11
CO/CO 2 Study of High Performance La 0.3 Sr 0.7 Fe 0.7 Cr 0.3 O 3- δ Reversible SOFC Electrodes
journal, September 2015
- Addo, P. K.; Molero-Sanchez, B.; Chen, M.
- Fuel Cells, Vol. 15, Issue 5
Hollow Nanocrystals through the Nanoscale Kirkendall Effect
journal, December 2012
- Wang, Wenshou; Dahl, Michael; Yin, Yadong
- Chemistry of Materials, Vol. 25, Issue 8
Novel cobalt-free BaFe 1−x Gd x O 3−δ perovskite membranes for oxygen separation
journal, January 2016
- Lu, Yao; Zhao, Hailei; Chang, Xiwang
- Journal of Materials Chemistry A, Vol. 4, Issue 27
In situ growth of nanoparticles through control of non-stoichiometry
journal, October 2013
- Neagu, Dragos; Tsekouras, George; Miller, David N.
- Nature Chemistry, Vol. 5, Issue 11
A dense La(Sr)Fe(Mn)O 3−δ nano-film anode for intermediate-temperature solid oxide fuel cells
journal, January 2015
- Ju, Young-Wan; Hyodo, Junji; Inoishi, Atsushi
- Journal of Materials Chemistry A, Vol. 3, Issue 7
Rhodium-Catalyzed Methanation and Methane Steam Reforming Reactions on Rhodium-Perovskite Systems: Metal-Support Interaction
journal, May 2016
- Thalinger, Ramona; Götsch, Thomas; Zhuo, Chen
- ChemCatChem, Vol. 8, Issue 12
The Nanoscale Kirkendall Effect in Pd-Based Intermetallic Phases
journal, July 2014
- Götsch, Thomas; Stöger-Pollach, Michael; Thalinger, Ramona
- The Journal of Physical Chemistry C, Vol. 118, Issue 31
Die Strukturen von Verbindungen ABO3 „Schwesterstrukturen.“
journal, September 1943
- v. Náray-Szabó, St.
- Naturwissenschaften, Vol. 31, Issue 39-40
New Insight into Hydrogen Oxidation Reaction on La 0.3 Sr 0.7 Fe 0.7 Cr 0.3 O 3-δ Perovskite as a Solid Oxide Fuel Cell Anode
journal, January 2017
- Chen, Min; Chen, Dongchu; Chang, Menglei
- Journal of The Electrochemical Society, Vol. 164, Issue 4
Ni doped La 0.6 Sr 0.4 FeO 3- δ symmetrical electrode for solid oxide fuel cells
journal, August 2016
- Ma, Zhaohui; Sun, Chunwen; Ma, Chao
- Chinese Journal of Catalysis, Vol. 37, Issue 8
Crystal structure, magnetic properties, and Mössbauer studies of prepared by quenching in different atmospheres
journal, November 2002
- Yang, J. B.; Yelon, W. B.; James, W. J.
- Physical Review B, Vol. 66, Issue 18
Advanced anodes for high-temperature fuel cells
journal, January 2004
- Atkinson, A.; Barnett, S.; Gorte, R. J.
- Nature Materials, Vol. 3, Issue 1
La 0.8 Sr 0.2 FeO 3−δ as Fuel Electrode for Solid Oxide Reversible Cells Using LaGaO 3 -Based Oxide Electrolyte
journal, May 2016
- Hosoi, Kohei; Hagiwara, Hidehisa; Ida, Shintaro
- The Journal of Physical Chemistry C, Vol. 120, Issue 29
The Crystal Chemistry and Physical Properties of the Triple Layer Perovskite Intergrowths LaSr3Fe3O10-δ and LaSr3(Fe3-xAlx)O10-δ
journal, March 1993
- Lee, J. Y.; Swinnea, J. S.; Steinfink, H.
- Journal of Solid State Chemistry, Vol. 103, Issue 1
Compact low power infrared tube furnace for in situ X-ray powder diffraction
journal, January 2017
- Doran, A.; Schlicker, L.; Beavers, C. M.
- Review of Scientific Instruments, Vol. 88, Issue 1
Iron Exsolution Phenomena in Lanthanum Strontium Ferrite SOFC Anodes
journal, May 2017
- Götsch, Thomas; Praty, Corsin; Grünbacher, Matthias
- ECS Transactions, Vol. 78, Issue 1
La(Sr)Fe(Mn)O3 Thin Film Anode for Improving Power Generating Property with Enhancing Electric Conductivity and Oxidation Activity
journal, October 2013
- Ju, Y. -W.; Ida, S.; Ishihara, T.
- ECS Transactions, Vol. 57, Issue 1
The Effect of Oxygen Stoichiometry on Phase Relations and Structure in the System La1-xSrxFeO3-δ (0 ≤ x ≤ 1, 0 ≤ δ ≤ 0.5)
journal, March 1994
- Dann, S. E.; Currie, D. B.; Weller, M. T.
- Journal of Solid State Chemistry, Vol. 109, Issue 1
Surface chemistry of pure tetragonal ZrO 2 and gas-phase dependence of the tetragonal-to-monoclinic ZrO 2 transformation
journal, January 2017
- Köck, Eva-Maria; Kogler, Michaela; Götsch, Thomas
- Dalton Transactions, Vol. 46, Issue 14
Crystal Structure and Thermal Expansion of La1−xSrxFeO3−δ Materials
journal, October 2004
- Fossdal, Anita; Menon, Mohan; Waernhus, Ivar
- Journal of the American Ceramic Society, Vol. 87, Issue 10
Enhancing Electrochemical Water-Splitting Kinetics by Polarization-Driven Formation of Near-Surface Iron(0): An In Situ XPS Study on Perovskite-Type Electrodes
journal, December 2014
- Opitz, Alexander K.; Nenning, Andreas; Rameshan, Christoph
- Angewandte Chemie, Vol. 127, Issue 9
Structural and Chemical Evolution of the SOFC Anode La 0.30 Sr 0.70 Fe 0.70 Cr 0.30 O 3−δ upon Reduction and Oxidation: An in Situ Neutron Diffraction Study
journal, May 2010
- Haag, Jacob M.; Barnett, Scott A.; Richardson, James W.
- Chemistry of Materials, Vol. 22, Issue 10
Effects of Firing and Reduction Conditions on Swelling and Iron Whisker Formation during the Reduction of Iron Oxide Compact
journal, January 2011
- Wang, Haitao; Sohn, Hong Yong
- ISIJ International, Vol. 51, Issue 6
Exsolution of Fe and SrO Nanorods and Nanoparticles from Lanthanum Strontium Ferrite La 0.6 Sr 0.4 FeO 3−δ Materials by Hydrogen Reduction
journal, September 2015
- Thalinger, Ramona; Gocyla, Martin; Heggen, Marc
- The Journal of Physical Chemistry C, Vol. 119, Issue 38
The lattice expansion of iron
journal, May 1955
- Basinski, Zbigniew Stanislaw; Hume-Rothery, William; Sutton, A. L.
- Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, Vol. 229, Issue 1179, p. 459-467
Solid Oxide Fuel Cell Fabricated Using All-Perovskite Materials
journal, January 2006
- Hsu, Meng-Fang; Wu, Lin-Jung; Wu, Jenn-Ming
- Electrochemical and Solid-State Letters, Vol. 9, Issue 4
Enhancing Electrochemical Water-Splitting Kinetics by Polarization-Driven Formation of Near-Surface Iron(0): An In Situ XPS Study on Perovskite-Type Electrodes
journal, December 2014
- Opitz, Alexander K.; Nenning, Andreas; Rameshan, Christoph
- Angewandte Chemie International Edition, Vol. 54, Issue 9
Works referencing / citing this record:
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journal, March 2020
- Lindenthal, Lorenz; Rameshan, Raffael; Summerer, Harald
- Catalysts, Vol. 10, Issue 3