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Title: Compositional and operational impacts on the thermochemical reduction of CO 2 to CO by iron oxide/yttria-stabilized zirconia

Abstract

Ferrites have potential for use as active materials in solar-thermochemical cycles because of their versatile redox chemistry. Such cycles utilize solar-thermal energy for the production of hydrogen from water and carbon monoxide from carbon dioxide. Although ferrites offer the potential for deep levels of reduction (e.g., stoichiometric conversion of magnetite to wüstite) and correspondingly large per-cycle product yields, in practice reactions are limited to surface regions made smaller by rapid sintering and agglomeration. Combining ferrites with zirconia or yttria-stabilized zirconia (YSZ) greatly improves the cyclability of the ferrites and enables a move away from powder to monolithic systems. We have studied the behavior of iron oxides composited with YSZ using thermogravimetric analysis under operando conditions. Samples in which the iron was fully dissolved within the YSZ matrix showed greater overall extent of thermochemical redox and higher rate of reaction than samples with equal iron loading but in which the iron was only partially dissolved, with the rest existing as agglomerates of iron oxide within the ceramic matrix. Varying the yttria content of the YSZ revealed a maximum thermochemical capacity (yield per cycle) for 6 mol% Y2O3 in YSZ. The first thermochemical redox cycle performed for each sample resulted in amore » net mass loss that was proportional to the iron oxide loading in the material and was stoichiometrically consistent with complete reduction of Fe2O3 to Fe3O4 and further partial reduction of the Fe3O4 to FeO. Mass gains upon reaction with CO2 were consistent with re-oxidation of the FeO fraction back to Fe3O4. The Fe dissolved in the YSZ matrix, however, is capable of cycling stoichiometrically between Fe3+ and Fe2+. Varying the re-oxidation temperature between 1000 and 1200 °C highlighted the trade-off between re-oxidation rate and equilibrium limitations.« less

Authors:
ORCiD logo [1];  [1];  [2]
  1. Sandia National Laboratories, Albuquerque, USA
  2. LightWorks®, Arizona State University, Tempe, USA
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1755792
Alternate Identifier(s):
OSTI ID: 1760457
Report Number(s):
SAND-2020-10146J
Journal ID: ISSN 2046-2069; RSCACL
Grant/Contract Number:  
AC04-94AL85000; NA0003525
Resource Type:
Published Article
Journal Name:
RSC Advances
Additional Journal Information:
Journal Name: RSC Advances Journal Volume: 11 Journal Issue: 3; Journal ID: ISSN 2046-2069
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Coker, Eric N., Ambrosini, Andrea, and Miller, James E. Compositional and operational impacts on the thermochemical reduction of CO 2 to CO by iron oxide/yttria-stabilized zirconia. United Kingdom: N. p., 2021. Web. doi:10.1039/D0RA08589H.
Coker, Eric N., Ambrosini, Andrea, & Miller, James E. Compositional and operational impacts on the thermochemical reduction of CO 2 to CO by iron oxide/yttria-stabilized zirconia. United Kingdom. https://doi.org/10.1039/D0RA08589H
Coker, Eric N., Ambrosini, Andrea, and Miller, James E. Tue . "Compositional and operational impacts on the thermochemical reduction of CO 2 to CO by iron oxide/yttria-stabilized zirconia". United Kingdom. https://doi.org/10.1039/D0RA08589H.
@article{osti_1755792,
title = {Compositional and operational impacts on the thermochemical reduction of CO 2 to CO by iron oxide/yttria-stabilized zirconia},
author = {Coker, Eric N. and Ambrosini, Andrea and Miller, James E.},
abstractNote = {Ferrites have potential for use as active materials in solar-thermochemical cycles because of their versatile redox chemistry. Such cycles utilize solar-thermal energy for the production of hydrogen from water and carbon monoxide from carbon dioxide. Although ferrites offer the potential for deep levels of reduction (e.g., stoichiometric conversion of magnetite to wüstite) and correspondingly large per-cycle product yields, in practice reactions are limited to surface regions made smaller by rapid sintering and agglomeration. Combining ferrites with zirconia or yttria-stabilized zirconia (YSZ) greatly improves the cyclability of the ferrites and enables a move away from powder to monolithic systems. We have studied the behavior of iron oxides composited with YSZ using thermogravimetric analysis under operando conditions. Samples in which the iron was fully dissolved within the YSZ matrix showed greater overall extent of thermochemical redox and higher rate of reaction than samples with equal iron loading but in which the iron was only partially dissolved, with the rest existing as agglomerates of iron oxide within the ceramic matrix. Varying the yttria content of the YSZ revealed a maximum thermochemical capacity (yield per cycle) for 6 mol% Y2O3 in YSZ. The first thermochemical redox cycle performed for each sample resulted in a net mass loss that was proportional to the iron oxide loading in the material and was stoichiometrically consistent with complete reduction of Fe2O3 to Fe3O4 and further partial reduction of the Fe3O4 to FeO. Mass gains upon reaction with CO2 were consistent with re-oxidation of the FeO fraction back to Fe3O4. The Fe dissolved in the YSZ matrix, however, is capable of cycling stoichiometrically between Fe3+ and Fe2+. Varying the re-oxidation temperature between 1000 and 1200 °C highlighted the trade-off between re-oxidation rate and equilibrium limitations.},
doi = {10.1039/D0RA08589H},
journal = {RSC Advances},
number = 3,
volume = 11,
place = {United Kingdom},
year = {Tue Jan 05 00:00:00 EST 2021},
month = {Tue Jan 05 00:00:00 EST 2021}
}

Journal Article:
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https://doi.org/10.1039/D0RA08589H

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