Giant onsite electronic entropy enhances the performance of ceria for water splitting

Naghavi, S. Shahab; Emery, Antoine A.; Hansen, Heine A.; Zhou, Fei; Ozolins, Vidvuds; Wolverton, Chris

doi:10.1038/s41467-017-00381-2

Giant onsite electronic entropy enhances the performance of ceria for water splitting

Journal Article · Fri Aug 18 04:00:00 EDT 2017 · Nature Communications

DOI:https://doi.org/10.1038/s41467-017-00381-2· OSTI ID:1395468

Naghavi, S. Shahab ^[1]; ^[1]; ^[2]; ^[3]; Ozolins, Vidvuds ^[4]; Wolverton, Chris ^[1]

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)

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 k_B 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.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC52-07NA27344; FG02-07ER46433

OSTI ID:: 1395468

Alternate ID(s):: OSTI ID: 1400078

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 8; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (51)

Hydrogen from water by reduced cerium oxide Otsuka, K. Journal of Catalysis, Vol. 79, Issue 2 https://doi.org/10.1016/0021-9517(83)90346-9	journal	February 1983
Mixed oxides of the type MO2 (fluorite)—M2O3—I oxygen dissociation pressures and phase relationships in the system CeO2Ce2O3 at high temperatures Bevan, D. J. M.; Kordis, J. Journal of Inorganic and Nuclear Chemistry, Vol. 26, Issue 9 https://doi.org/10.1016/0022-1902(64)80038-5	journal	September 1964
A thermodynamic study of nonstoichiometric cerium dioxide Panlener, R. J.; Blumenthal, R. N.; Garnier, J. E. Journal of Physics and Chemistry of Solids, Vol. 36, Issue 11, p. 1213-1222 https://doi.org/10.1016/0022-3697(75)90192-4	journal	November 1975
Small polaron electron transport in reduced CeO2 single crystals Tuller, H. L.; Nowick, A. S. Journal of Physics and Chemistry of Solids, Vol. 38, Issue 8 https://doi.org/10.1016/0022-3697(77)90124-x	journal	January 1977
Estimation of the standard entropy change on complete reduction of oxide MmOn Nakamura, Tetsurō Journal of Solid State Chemistry, Vol. 36, Issue 2 https://doi.org/10.1016/0022-4596(81)90162-6	journal	February 1981
Ceria-based solid electrolytes Inaba, H. Solid State Ionics, Vol. 83, Issue 1-2 https://doi.org/10.1016/0167-2738(95)00229-4	journal	January 1996
Use of CeO2-based oxides in the three-way catalysis Kašpar, J.; Fornasiero, P.; Graziani, M. Catalysis Today, Vol. 50, Issue 2 https://doi.org/10.1016/s0920-5861(98)00510-0	journal	April 1999
Vaporization thermodynamics of lanthanide trihalides Myers, Clifford E.; Graves, Dana T. Journal of Chemical & Engineering Data, Vol. 22, Issue 4 https://doi.org/10.1021/je60075a023	journal	October 1977
Materials for fuel-cell technologies Steele, Brian C. H.; Heinzel, Angelika Nature, Vol. 414, Issue 6861, p. 345-352 https://doi.org/10.1038/35104620	journal	November 2001
Nanostructured ceria-based materials: synthesis, properties, and applications Sun, Chunwen; Li, Hong; Chen, Liquan Energy & Environmental Science, Vol. 5, Issue 9 https://doi.org/10.1039/c2ee22310d	journal	January 2012
Entropies of defect formation in ceria from first principles Grieshammer, Steffen; Zacherle, Tobias; Martin, Manfred Physical Chemistry Chemical Physics, Vol. 15, Issue 38 https://doi.org/10.1039/c3cp51913a	journal	January 2013
CCCLI.—An investigation on the ceria–thoria catalysts Goggs, A. B. J. Chem. Soc., Vol. 0, Issue 0 https://doi.org/10.1039/jr9280002667	journal	January 1928
A thermochemical study of ceria: exploiting an old material for new modes of energy conversion and CO ₂ mitigation Chueh, William C.; Haile, Sossina M. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 368, Issue 1923 https://doi.org/10.1098/rsta.2010.0114	journal	July 2010
Temperature-Dependent Crystal Field and Hyperfine Interactions Walsh, Walter M.; Jeener, Jean; Bloembergen, N. Physical Review, Vol. 139, Issue 4A https://doi.org/10.1103/physrev.139.a1338	journal	August 1965
Obtaining correct orbital ground states in f -electron systems using a nonspherical self-interaction-corrected LDA + U method Zhou, Fei; Ozoliņš, V. Physical Review B, Vol. 80, Issue 12 https://doi.org/10.1103/physrevb.80.125127	journal	September 2009
Self-consistent density functional calculations of the crystal field levels in lanthanide and actinide dioxides Zhou, Fei; Ozoliņš, Vidvuds Physical Review B, Vol. 85, Issue 7 https://doi.org/10.1103/physrevb.85.075124	journal	February 2012
The Effects of Morphology on the Oxidation of Ceria by Water and Carbon Dioxide Venstrom, Luke J.; Petkovich, Nicholas; Rudisill, Stephen Journal of Solar Energy Engineering, Vol. 134, Issue 1 https://doi.org/10.1115/1.4005119	journal	November 2011
Renewable Hydrogen from Ethanol by Autothermal Reforming Deluga, G. A. Science, Vol. 303, Issue 5660 https://doi.org/10.1126/science.1093045	journal	February 2004
High-Flux Solar-Driven Thermochemical Dissociation of CO2 and H2O Using Nonstoichiometric Ceria Chueh, W. C.; Falter, C.; Abbott, M. Science, Vol. 330, Issue 6012 https://doi.org/10.1126/science.1197834	journal	December 2010
General Factors Governing the Efficiency of Luminescent Devices Yen, W. M. Physics of the Solid State, Vol. 47, Issue 8 https://doi.org/10.1134/1.2014476	journal	January 2005
Solar Thermochemical Hydrogen Production via Terbium Oxide Based Redox Reactions Bhosale, Rahul; Kumar, Anand; AlMomani, Fares International Journal of Photoenergy, Vol. 2016 https://doi.org/10.1155/2016/9727895	journal	January 2016
Materials-Related Aspects of Thermochemical Water and Carbon Dioxide Splitting: A Review Roeb, Martin; Neises, Martina; Monnerie, Nathalie Materials, Vol. 5, Issue 11, p. 2015-2054 https://doi.org/10.3390/ma5112015	journal	October 2012
Template-assisted formation of microsized nanocrystalline CeO ₂ tubes and their catalytic performance in the carboxylation of methanol Schneider, Jörg J.; Naumann, Meike; Schäfer, Christian Beilstein Journal of Nanotechnology, Vol. 2 https://doi.org/10.3762/bjnano.2.86	journal	January 2011
Evidence for Oxidation of Ceria by CO2 Sharma, S.; Hilaire, S.; Vohs, J. M. Journal of Catalysis, Vol. 190, Issue 1 https://doi.org/10.1006/jcat.1999.2746	journal	February 2000
Ceria in automotive exhaust catalysts I. Oxygen storage Yao, H. Journal of Catalysis, Vol. 86, Issue 2 https://doi.org/10.1016/0021-9517(84)90371-3	journal	April 1984
Small polaron electron transport in reduced CeO2 single crystals Tuller, H. L.; Nowick, A. S. Journal of Physics and Chemistry of Solids, Vol. 38, Issue 8 https://doi.org/10.1016/0022-3697(77)90124-X	journal	January 1977
Automotive exhaust catalysis Gandhi, H. S.; Graham, G. W.; McCabe, R. W. Journal of Catalysis, Vol. 216, Issue 1-2 https://doi.org/10.1016/S0021-9517(02)00067-2	journal	May 2003
Physical, chemical and electrochemical properties of pure and doped ceria Mogensen, M. Solid State Ionics, Vol. 129, Issue 1-4 https://doi.org/10.1016/S0167-2738(99)00318-5	journal	April 2000
Appraisal of Ce1−yGdyO2−y/2 electrolytes for IT-SOFC operation at 500°C Steele, B. Solid State Ionics, Vol. 129, Issue 1-4 https://doi.org/10.1016/S0167-2738(99)00319-7	journal	April 2000
Use of CeO2-based oxides in the three-way catalysis Kašpar, J.; Fornasiero, P.; Graziani, M. Catalysis Today, Vol. 50, Issue 2 https://doi.org/10.1016/S0920-5861(98)00510-0	journal	April 1999
Ab initio calculations on the local structure and the 4f–5d absorption and emission spectra of -doped YAG Gracia, Jose; Seijo, Luis; Barandiarán, Zoila Journal of Luminescence, Vol. 128, Issue 8 https://doi.org/10.1016/j.jlumin.2007.12.027	journal	August 2008
Thermochemical hydrogen production from a two-step solar-driven water-splitting cycle based on cerium oxides Abanades, Stéphane; Flamant, Gilles Solar Energy, Vol. 80, Issue 12 https://doi.org/10.1016/j.solener.2005.12.005	journal	December 2006
Direct oxidation of hydrocarbons in a solid-oxide fuel cell Park, Seungdoo; Vohs, John M.; Gorte, Raymond J. Nature, Vol. 404, Issue 6775 https://doi.org/10.1038/35005040	journal	March 2000
CCCLI.—An investigation on the ceria–thoria catalysts Goggs, A. B. J. Chem. Soc., Vol. 0, Issue 0 https://doi.org/10.1039/JR9280002667	journal	January 1928
Thermodynamics of solid electrolytes and related oxide ceramics based on the fluorite structure Navrotsky, Alexandra Journal of Materials Chemistry, Vol. 20, Issue 47 https://doi.org/10.1039/c0jm01521k	journal	January 2010
New Regularities in the Spectra of the Alkaline Earths Russell, H. N.; Saunders, F. A. The Astrophysical Journal, Vol. 61 https://doi.org/10.1086/142872	journal	January 1925
Extraction of crystal-field parameters for lanthanide ions from quantum-chemical calculations Hu, Liusen; Reid, Michael F.; Duan, Chang-Kui Journal of Physics: Condensed Matter, Vol. 23, Issue 4 https://doi.org/10.1088/0953-8984/23/4/045501	journal	January 2011
Temperature-Dependent Crystal Field and Hyperfine Interactions Walsh, Walter M.; Jeener, Jean; Bloembergen, N. Physical Review, Vol. 139, Issue 4A https://doi.org/10.1103/PhysRev.139.A1338	journal	August 1965
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
4 f n → 4 f n − 1 5 d transitions of the light lanthanides: Experiment and theory van Pieterson, L.; Reid, M. F.; Wegh, R. T. Physical Review B, Vol. 65, Issue 4 https://doi.org/10.1103/PhysRevB.65.045113	journal	January 2002
Obtaining correct orbital ground states in f -electron systems using a nonspherical self-interaction-corrected LDA + U method Zhou, Fei; Ozoliņš, V. Physical Review B, Vol. 80, Issue 12 https://doi.org/10.1103/PhysRevB.80.125127	journal	September 2009
First-principles thermodynamic framework for the evaluation of thermochemical H 2 O - or CO 2 -splitting materials Meredig, B.; Wolverton, C. Physical Review B, Vol. 80, Issue 24 https://doi.org/10.1103/PhysRevB.80.245119	journal	December 2009
Self-consistent density functional calculations of the crystal field levels in lanthanide and actinide dioxides Zhou, Fei; Ozoliņš, Vidvuds Physical Review B, Vol. 85, Issue 7 https://doi.org/10.1103/PhysRevB.85.075124	journal	February 2012
Ab initio thermodynamics of intrinsic oxygen vacancies in ceria Gopal, Chirranjeevi Balaji; van de Walle, Axel Physical Review B, Vol. 86, Issue 13 https://doi.org/10.1103/PhysRevB.86.134117	journal	October 2012
Crystal-field interaction and oxygen stoichiometry effects in strontium-doped rare-earth cobaltates Furrer, A.; Podlesnyak, A.; Frontzek, M. Physical Review B, Vol. 90, Issue 6 https://doi.org/10.1103/PhysRevB.90.064426	journal	August 2014
Ordering of oxygen vacancies and excess charge localization in bulk ceria: A DFT + U study Murgida, G. E.; Ferrari, V.; Ganduglia-Pirovano, M. Verónica Physical Review B, Vol. 90, Issue 11 https://doi.org/10.1103/PhysRevB.90.115120	journal	September 2014
Crystal-field calculations for transition-metal ions by application of an opposing potential Zhou, Fei; Åberg, Daniel Physical Review B, Vol. 93, Issue 8 https://doi.org/10.1103/PhysRevB.93.085123	journal	February 2016
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Configurational Electronic Entropy and the Phase Diagram of Mixed-Valence Oxides: The Case of Li x FePO 4 Zhou, Fei; Maxisch, Thomas; Ceder, Gerbrand Physical Review Letters, Vol. 97, Issue 15 https://doi.org/10.1103/PhysRevLett.97.155704	journal	October 2006
Defect Structure and Electrical Properties of Nonstoichiometric CeO[sub 2] Single Crystals Tuller, H. L. Journal of The Electrochemical Society, Vol. 126, Issue 2 https://doi.org/10.1149/1.2129007	journal	January 1979

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