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

S. Shahab Naghavi, Antoine A. Emery, Heine A. Hansen, Fei Zhou, Vidvuds Ozolins and Chris Wolverton ()
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S. Shahab Naghavi: Northwestern University
Antoine A. Emery: Northwestern University
Heine A. Hansen: Technical University of Denmark
Fei Zhou: Lawrence Livermore National Laboratory
Vidvuds Ozolins: Department of Applied Physics, Yale University
Chris Wolverton: Northwestern University

Nature Communications, 2017, vol. 8, issue 1, 1-6

Abstract: 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 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.

Date: 2017
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DOI: 10.1038/s41467-017-00381-2

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