Favorable Redox Thermodynamics of SrTi0.5Mn0.5O3–δ in Solar Thermochemical Water Splitting
Abstract
Two-step, solar thermochemical splitting of water using nonstoichiometric redox-active metal oxides has emerged as an intriguing approach for large-scale hydrogen production. Perovskites have been proposed as alternatives to state-of-the-art fluorite CeO2–δ because of their potential for lowering reduction temperature while maintaining high fuel productivity. Guided by computational insights, we explore the thermodynamic properties and water splitting efficacy of the cubic perovskite SrTi0.5Mn0.5O3–δ (STM55). Thermogravimetric analysis is performed under controlled oxygen partial pressures (pO2) and temperatures up to 1500 °C, from which both the enthalpy and entropy of reduction as a function of oxygen nonstoichiometry are determined. STM55 provides an attractive combination of moderate enthalpy, 200–250 kJ (mol-O)–1, and high entropy, with unusual δ dependence. Using a water splitting cycle in which the material is thermally reduced at 1350 °C (pO2, ~10–5 atm) and subsequently exposed to steam at 1100 °C (steam partial pressure of pH2O = 0.4 atm), we demonstrate a hydrogen yield of 7.4 mL g–1. Through both half-cycles, the material remains largely in quasi-equilibrium with the gas phase, as reflected in the agreement of the measured data with predicted profiles based on the thermodynamic data. This behavior indicates rapid surface and bulk diffusion kinetics. Cyclic operation showed themore »
- Authors:
-
[1];
[1];
[1];
[1]
- Northwestern Univ., Evanston, IL (United States)
- Northwestern Univ., Evanston, IL (United States); Inst. of Catalysis and Petrochemistry, Madrid (Spain)
- Publication Date:
- Research Org.:
- Northwestern Univ., Evanston, IL (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE)
- OSTI Identifier:
- 1880997
- Alternate Identifier(s):
- OSTI ID: 1985157
- Grant/Contract Number:
- EE0008089
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 32; Journal Issue: 21; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Fuels; Hydrogen; Materials; Oxygen; Redox reactions
Citation Formats
Qian, Xin, He, Jiangang, Mastronardo, Emanuela, Baldassarri, Bianca, Wolverton, Christopher, and Haile, Sossina M. Favorable Redox Thermodynamics of SrTi0.5Mn0.5O3–δ in Solar Thermochemical Water Splitting. United States: N. p., 2020.
Web. doi:10.1021/acs.chemmater.0c03278.
Qian, Xin, He, Jiangang, Mastronardo, Emanuela, Baldassarri, Bianca, Wolverton, Christopher, & Haile, Sossina M. Favorable Redox Thermodynamics of SrTi0.5Mn0.5O3–δ in Solar Thermochemical Water Splitting. United States. https://doi.org/10.1021/acs.chemmater.0c03278
Qian, Xin, He, Jiangang, Mastronardo, Emanuela, Baldassarri, Bianca, Wolverton, Christopher, and Haile, Sossina M. Mon .
"Favorable Redox Thermodynamics of SrTi0.5Mn0.5O3–δ in Solar Thermochemical Water Splitting". United States. https://doi.org/10.1021/acs.chemmater.0c03278. https://www.osti.gov/servlets/purl/1880997.
@article{osti_1880997,
title = {Favorable Redox Thermodynamics of SrTi0.5Mn0.5O3–δ in Solar Thermochemical Water Splitting},
author = {Qian, Xin and He, Jiangang and Mastronardo, Emanuela and Baldassarri, Bianca and Wolverton, Christopher and Haile, Sossina M.},
abstractNote = {Two-step, solar thermochemical splitting of water using nonstoichiometric redox-active metal oxides has emerged as an intriguing approach for large-scale hydrogen production. Perovskites have been proposed as alternatives to state-of-the-art fluorite CeO2–δ because of their potential for lowering reduction temperature while maintaining high fuel productivity. Guided by computational insights, we explore the thermodynamic properties and water splitting efficacy of the cubic perovskite SrTi0.5Mn0.5O3–δ (STM55). Thermogravimetric analysis is performed under controlled oxygen partial pressures (pO2) and temperatures up to 1500 °C, from which both the enthalpy and entropy of reduction as a function of oxygen nonstoichiometry are determined. STM55 provides an attractive combination of moderate enthalpy, 200–250 kJ (mol-O)–1, and high entropy, with unusual δ dependence. Using a water splitting cycle in which the material is thermally reduced at 1350 °C (pO2, ~10–5 atm) and subsequently exposed to steam at 1100 °C (steam partial pressure of pH2O = 0.4 atm), we demonstrate a hydrogen yield of 7.4 mL g–1. Through both half-cycles, the material remains largely in quasi-equilibrium with the gas phase, as reflected in the agreement of the measured data with predicted profiles based on the thermodynamic data. This behavior indicates rapid surface and bulk diffusion kinetics. Cyclic operation showed the material to be free of degradation and always resulted in a 2:1 yield of H2/O2. Altogether, STM55 provides outstanding performance characteristics for thermochemical hydrogen production.},
doi = {10.1021/acs.chemmater.0c03278},
journal = {Chemistry of Materials},
number = 21,
volume = 32,
place = {United States},
year = {Mon Oct 26 00:00:00 EDT 2020},
month = {Mon Oct 26 00:00:00 EDT 2020}
}
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