Giant onsite electronic entropy enhances the performance of ceria for water splitting
Abstract
Previous studies have shown that a large solid-state entropy of reduction increases the thermodynamic efficiency of metal oxides, such as ceria, for two-step thermochemical water splitting cycles. In this context, the configurational entropy arising from oxygen off-stoichiometry in the oxide, has been the focus of most previous work. Here we report a different source of entropy, the onsite electronic configurational entropy, arising from coupling between orbital and spin angular momenta in lanthanide f orbitals. We find that onsite electronic configurational entropy is sizable in all lanthanides, and reaches a maximum value of ≈4.7 kB per oxygen vacancy for Ce4+/Ce3+ reduction. This unique and large positive entropy source in ceria explains its excellent performance for high-temperature catalytic redox reactions such as water splitting. Our calculations also show that terbium dioxide has a high electronic entropy and thus could also be a potential candidate for solar thermochemical reactions.
- Authors:
-
- Northwestern Univ., Evanston, IL (United States). Department of Materials Science and Engineering
- Technical University of Denmark (Denmark). Department of Energy Conversion and Storage
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Yale Univ., New Haven, CT (United States). Department of Applied Physics; Yale Energy Sciences Institute, West Haven, CT (United States)
- Publication Date:
- Research Org.:
- Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1395468
- Grant/Contract Number:
- AC52-07NA27344; FG02-07ER46433
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Communications
- Additional Journal Information:
- Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2041-1723
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Computational methods; Electronic structure; Energy modelling
Citation Formats
Naghavi, S. Shahab, Emery, Antoine A., Hansen, Heine A., Zhou, Fei, Ozolins, Vidvuds, and Wolverton, Chris. Giant onsite electronic entropy enhances the performance of ceria for water splitting. United States: N. p., 2017.
Web. doi:10.1038/s41467-017-00381-2.
Naghavi, S. Shahab, Emery, Antoine A., Hansen, Heine A., Zhou, Fei, Ozolins, Vidvuds, & Wolverton, Chris. Giant onsite electronic entropy enhances the performance of ceria for water splitting. United States. https://doi.org/10.1038/s41467-017-00381-2
Naghavi, S. Shahab, Emery, Antoine A., Hansen, Heine A., Zhou, Fei, Ozolins, Vidvuds, and Wolverton, Chris. Fri .
"Giant onsite electronic entropy enhances the performance of ceria for water splitting". United States. https://doi.org/10.1038/s41467-017-00381-2. https://www.osti.gov/servlets/purl/1395468.
@article{osti_1395468,
title = {Giant onsite electronic entropy enhances the performance of ceria for water splitting},
author = {Naghavi, S. Shahab and Emery, Antoine A. and Hansen, Heine A. and Zhou, Fei and Ozolins, Vidvuds and Wolverton, Chris},
abstractNote = {Previous studies have shown that a large solid-state entropy of reduction increases the thermodynamic efficiency of metal oxides, such as ceria, for two-step thermochemical water splitting cycles. In this context, the configurational entropy arising from oxygen off-stoichiometry in the oxide, has been the focus of most previous work. Here we report a different source of entropy, the onsite electronic configurational entropy, arising from coupling between orbital and spin angular momenta in lanthanide f orbitals. We find that onsite electronic configurational entropy is sizable in all lanthanides, and reaches a maximum value of ≈4.7 kB per oxygen vacancy for Ce4+/Ce3+ reduction. This unique and large positive entropy source in ceria explains its excellent performance for high-temperature catalytic redox reactions such as water splitting. Our calculations also show that terbium dioxide has a high electronic entropy and thus could also be a potential candidate for solar thermochemical reactions.},
doi = {10.1038/s41467-017-00381-2},
journal = {Nature Communications},
number = 1,
volume = 8,
place = {United States},
year = {Fri Aug 18 00:00:00 EDT 2017},
month = {Fri Aug 18 00:00:00 EDT 2017}
}
Web of Science
Works referenced in this record:
Nanostructured ceria-based materials: synthesis, properties, and applications
journal, January 2012
- Sun, Chunwen; Li, Hong; Chen, Liquan
- Energy & Environmental Science, Vol. 5, Issue 9
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Entropies of defect formation in ceria from first principles
journal, January 2013
- Grieshammer, Steffen; Zacherle, Tobias; Martin, Manfred
- Physical Chemistry Chemical Physics, Vol. 15, Issue 38
Configurational Electronic Entropy and the Phase Diagram of Mixed-Valence Oxides: The Case of
journal, October 2006
- Zhou, Fei; Maxisch, Thomas; Ceder, Gerbrand
- Physical Review Letters, Vol. 97, Issue 15
Evidence for Oxidation of Ceria by CO2
journal, February 2000
- Sharma, S.; Hilaire, S.; Vohs, J. M.
- Journal of Catalysis, Vol. 190, Issue 1
Ceria in automotive exhaust catalysts I. Oxygen storage
journal, April 1984
- Yao, H.
- Journal of Catalysis, Vol. 86, Issue 2
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Materials for fuel-cell technologies
journal, November 2001
- Steele, Brian C. H.; Heinzel, Angelika
- Nature, Vol. 414, Issue 6861, p. 345-352
Crystal-field calculations for transition-metal ions by application of an opposing potential
journal, February 2016
- Zhou, Fei; Åberg, Daniel
- Physical Review B, Vol. 93, Issue 8
The Effects of Morphology on the Oxidation of Ceria by Water and Carbon Dioxide
journal, November 2011
- Venstrom, Luke J.; Petkovich, Nicholas; Rudisill, Stephen
- Journal of Solar Energy Engineering, Vol. 134, Issue 1
Template-assisted formation of microsized nanocrystalline CeO 2 tubes and their catalytic performance in the carboxylation of methanol
journal, January 2011
- Schneider, Jörg J.; Naumann, Meike; Schäfer, Christian
- Beilstein Journal of Nanotechnology, Vol. 2
Thermochemical hydrogen production from a two-step solar-driven water-splitting cycle based on cerium oxides
journal, December 2006
- Abanades, Stéphane; Flamant, Gilles
- Solar Energy, Vol. 80, Issue 12
Ceria-based solid electrolytes
journal, January 1996
- Inaba, H.
- Solid State Ionics, Vol. 83, Issue 1-2
A thermochemical study of ceria: exploiting an old material for new modes of energy conversion and CO 2 mitigation
journal, July 2010
- Chueh, William C.; Haile, Sossina M.
- Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 368, Issue 1923
New Regularities in the Spectra of the Alkaline Earths
journal, January 1925
- Russell, H. N.; Saunders, F. A.
- The Astrophysical Journal, Vol. 61
Crystal-field interaction and oxygen stoichiometry effects in strontium-doped rare-earth cobaltates
journal, August 2014
- Furrer, A.; Podlesnyak, A.; Frontzek, M.
- Physical Review B, Vol. 90, Issue 6
Ab initio calculations on the local structure and the 4f–5d absorption and emission spectra of -doped YAG
journal, August 2008
- Gracia, Jose; Seijo, Luis; Barandiarán, Zoila
- Journal of Luminescence, Vol. 128, Issue 8
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Hydrogen from water by reduced cerium oxide
journal, February 1983
- Otsuka, K.
- Journal of Catalysis, Vol. 79, Issue 2
Automotive exhaust catalysis
journal, May 2003
- Gandhi, H. S.; Graham, G. W.; McCabe, R. W.
- Journal of Catalysis, Vol. 216, Issue 1-2
Defect Structure and Electrical Properties of Nonstoichiometric CeO[sub 2] Single Crystals
journal, January 1979
- Tuller, H. L.
- Journal of The Electrochemical Society, Vol. 126, Issue 2
Estimation of the standard entropy change on complete reduction of oxide MmOn
journal, February 1981
- Nakamura, Tetsurō
- Journal of Solid State Chemistry, Vol. 36, Issue 2
transitions of the light lanthanides: Experiment and theory
journal, January 2002
- van Pieterson, L.; Reid, M. F.; Wegh, R. T.
- Physical Review B, Vol. 65, Issue 4
A thermodynamic study of nonstoichiometric cerium dioxide
journal, November 1975
- Panlener, R. J.; Blumenthal, R. N.; Garnier, J. E.
- Journal of Physics and Chemistry of Solids, Vol. 36, Issue 11, p. 1213-1222
Vaporization thermodynamics of lanthanide trihalides
journal, October 1977
- Myers, Clifford E.; Graves, Dana T.
- Journal of Chemical & Engineering Data, Vol. 22, Issue 4
Extraction of crystal-field parameters for lanthanide ions from quantum-chemical calculations
journal, January 2011
- Hu, Liusen; Reid, Michael F.; Duan, Chang-Kui
- Journal of Physics: Condensed Matter, Vol. 23, Issue 4
Materials-Related Aspects of Thermochemical Water and Carbon Dioxide Splitting: A Review
journal, October 2012
- Roeb, Martin; Neises, Martina; Monnerie, Nathalie
- Materials, Vol. 5, Issue 11, p. 2015-2054
Solar Thermochemical Hydrogen Production via Terbium Oxide Based Redox Reactions
journal, January 2016
- Bhosale, Rahul; Kumar, Anand; AlMomani, Fares
- International Journal of Photoenergy, Vol. 2016
Direct oxidation of hydrocarbons in a solid-oxide fuel cell
journal, March 2000
- Park, Seungdoo; Vohs, John M.; Gorte, Raymond J.
- Nature, Vol. 404, Issue 6775
Thermodynamics of solid electrolytes and related oxide ceramics based on the fluorite structure
journal, January 2010
- Navrotsky, Alexandra
- Journal of Materials Chemistry, Vol. 20, Issue 47
Appraisal of Ce1−yGdyO2−y/2 electrolytes for IT-SOFC operation at 500°C
journal, April 2000
- Steele, B.
- Solid State Ionics, Vol. 129, Issue 1-4
Ordering of oxygen vacancies and excess charge localization in bulk ceria: A study
journal, September 2014
- Murgida, G. E.; Ferrari, V.; Ganduglia-Pirovano, M. Verónica
- Physical Review B, Vol. 90, Issue 11
General Factors Governing the Efficiency of Luminescent Devices
journal, January 2005
- Yen, W. M.
- Physics of the Solid State, Vol. 47, Issue 8
Renewable Hydrogen from Ethanol by Autothermal Reforming
journal, February 2004
- Deluga, G. A.
- Science, Vol. 303, Issue 5660
Mixed oxides of the type MO2 (fluorite)—M2O3—I oxygen dissociation pressures and phase relationships in the system CeO2Ce2O3 at high temperatures
journal, September 1964
- Bevan, D. J. M.; Kordis, J.
- Journal of Inorganic and Nuclear Chemistry, Vol. 26, Issue 9
High-Flux Solar-Driven Thermochemical Dissociation of CO2 and H2O Using Nonstoichiometric Ceria
journal, December 2010
- Chueh, W. C.; Falter, C.; Abbott, M.
- Science, Vol. 330, Issue 6012
Physical, chemical and electrochemical properties of pure and doped ceria
journal, April 2000
- Mogensen, M.
- Solid State Ionics, Vol. 129, Issue 1-4
Hydrogen from water by reduced cerium oxide
journal, February 1983
- Otsuka, K.
- Journal of Catalysis, Vol. 79, Issue 2
Mixed oxides of the type MO2 (fluorite)—M2O3—I oxygen dissociation pressures and phase relationships in the system CeO2Ce2O3 at high temperatures
journal, September 1964
- Bevan, D. J. M.; Kordis, J.
- Journal of Inorganic and Nuclear Chemistry, Vol. 26, Issue 9
A thermodynamic study of nonstoichiometric cerium dioxide
journal, November 1975
- Panlener, R. J.; Blumenthal, R. N.; Garnier, J. E.
- Journal of Physics and Chemistry of Solids, Vol. 36, Issue 11, p. 1213-1222
Small polaron electron transport in reduced CeO2 single crystals
journal, January 1977
- Tuller, H. L.; Nowick, A. S.
- Journal of Physics and Chemistry of Solids, Vol. 38, Issue 8
Estimation of the standard entropy change on complete reduction of oxide MmOn
journal, February 1981
- Nakamura, Tetsurō
- Journal of Solid State Chemistry, Vol. 36, Issue 2
Ceria-based solid electrolytes
journal, January 1996
- Inaba, H.
- Solid State Ionics, Vol. 83, Issue 1-2
Use of CeO2-based oxides in the three-way catalysis
journal, April 1999
- Kašpar, J.; Fornasiero, P.; Graziani, M.
- Catalysis Today, Vol. 50, Issue 2
Vaporization thermodynamics of lanthanide trihalides
journal, October 1977
- Myers, Clifford E.; Graves, Dana T.
- Journal of Chemical & Engineering Data, Vol. 22, Issue 4
Materials for fuel-cell technologies
journal, November 2001
- Steele, Brian C. H.; Heinzel, Angelika
- Nature, Vol. 414, Issue 6861, p. 345-352
Nanostructured ceria-based materials: synthesis, properties, and applications
journal, January 2012
- Sun, Chunwen; Li, Hong; Chen, Liquan
- Energy & Environmental Science, Vol. 5, Issue 9
Entropies of defect formation in ceria from first principles
journal, January 2013
- Grieshammer, Steffen; Zacherle, Tobias; Martin, Manfred
- Physical Chemistry Chemical Physics, Vol. 15, Issue 38
CCCLI.—An investigation on the ceria–thoria catalysts
journal, January 1928
- Goggs, A. B.
- J. Chem. Soc., Vol. 0, Issue 0
A thermochemical study of ceria: exploiting an old material for new modes of energy conversion and CO 2 mitigation
journal, July 2010
- Chueh, William C.; Haile, Sossina M.
- Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 368, Issue 1923
Temperature-Dependent Crystal Field and Hyperfine Interactions
journal, August 1965
- Walsh, Walter M.; Jeener, Jean; Bloembergen, N.
- Physical Review, Vol. 139, Issue 4A
Obtaining correct orbital ground states in -electron systems using a nonspherical self-interaction-corrected method
journal, September 2009
- Zhou, Fei; Ozoliņš, V.
- Physical Review B, Vol. 80, Issue 12
Self-consistent density functional calculations of the crystal field levels in lanthanide and actinide dioxides
journal, February 2012
- Zhou, Fei; Ozoliņš, Vidvuds
- Physical Review B, Vol. 85, Issue 7
The Effects of Morphology on the Oxidation of Ceria by Water and Carbon Dioxide
journal, November 2011
- Venstrom, Luke J.; Petkovich, Nicholas; Rudisill, Stephen
- Journal of Solar Energy Engineering, Vol. 134, Issue 1
Renewable Hydrogen from Ethanol by Autothermal Reforming
journal, February 2004
- Deluga, G. A.
- Science, Vol. 303, Issue 5660
High-Flux Solar-Driven Thermochemical Dissociation of CO2 and H2O Using Nonstoichiometric Ceria
journal, December 2010
- Chueh, W. C.; Falter, C.; Abbott, M.
- Science, Vol. 330, Issue 6012
General Factors Governing the Efficiency of Luminescent Devices
journal, January 2005
- Yen, W. M.
- Physics of the Solid State, Vol. 47, Issue 8
Solar Thermochemical Hydrogen Production via Terbium Oxide Based Redox Reactions
journal, January 2016
- Bhosale, Rahul; Kumar, Anand; AlMomani, Fares
- International Journal of Photoenergy, Vol. 2016
Materials-Related Aspects of Thermochemical Water and Carbon Dioxide Splitting: A Review
journal, October 2012
- Roeb, Martin; Neises, Martina; Monnerie, Nathalie
- Materials, Vol. 5, Issue 11, p. 2015-2054
Template-assisted formation of microsized nanocrystalline CeO 2 tubes and their catalytic performance in the carboxylation of methanol
journal, January 2011
- Schneider, Jörg J.; Naumann, Meike; Schäfer, Christian
- Beilstein Journal of Nanotechnology, Vol. 2
Works referencing / citing this record:
Stabilization of the Oxidation State +IV in Siloxide‐Supported Terbium Compounds
journal, February 2020
- Willauer, Aurélien R.; Palumbo, Chad T.; Scopelliti, Rosario
- Angewandte Chemie International Edition, Vol. 59, Issue 9
Dynamic charge and oxidation state of Pt/CeO2 single-atom catalysts
journal, August 2019
- Daelman, Nathan; Capdevila-Cortada, Marçal; López, Núria
- Nature Materials, Vol. 18, Issue 11
The use of poly-cation oxides to lower the temperature of two-step thermochemical water splitting
journal, January 2018
- Zhai, Shang; Rojas, Jimmy; Ahlborg, Nadia
- Energy & Environmental Science, Vol. 11, Issue 8
BaCe 0.25 Mn 0.75 O 3−δ —a promising perovskite-type oxide for solar thermochemical hydrogen production
journal, January 2018
- R. Barcellos, Debora; Sanders, Michael D.; Tong, Jianhua
- Energy & Environmental Science, Vol. 11, Issue 11
CeO 2−x quantum dots with massive oxygen vacancies as efficient catalysts for the synthesis of dimethyl carbonate
journal, January 2020
- Wang, Zhi-Qiao; Zhang, Ming-Jian; Hu, Xiao-Bing
- Chemical Communications, Vol. 56, Issue 3
Communication: The electronic entropy of charged defect formation and its impact on thermochemical redox cycles
journal, February 2018
- Lany, Stephan
- The Journal of Chemical Physics, Vol. 148, Issue 7
Ab initio calculation of the migration free energy of oxygen diffusion in pure and samarium-doped ceria
journal, January 2018
- Koettgen, Julius; Schmidt, Peter C.; Bučko, Tomáš
- Physical Review B, Vol. 97, Issue 2
Stabilization of the Oxidation State +IV in Siloxide‐Supported Terbium Compounds
journal, January 2020
- Willauer, Aurélien R.; Palumbo, Chad T.; Scopelliti, Rosario
- Angewandte Chemie, Vol. 132, Issue 9
Ab initio calculation of the migration free energy of oxygen diffusion in pure and samarium-doped ceria
text, January 2018
- Köttgen, Julius Rütger; Schmidt, Peter C.; Bučko, Tomáš
- RWTH Aachen University
A review of defect structure and chemistry in ceria and its solid solutions
text, January 2020
- Schmitt, Rafael; Nenning, Andreas; Kraynis, Olga
- ETH Zurich