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, Chris Wolverton*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

46 Scopus citations


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.

Original languageEnglish (US)
Article number285
JournalNature communications
Issue number1
StatePublished - Dec 1 2017

ASJC Scopus subject areas

  • General Physics and Astronomy
  • General Chemistry
  • General Biochemistry, Genetics and Molecular Biology


Dive into the research topics of 'Giant onsite electronic entropy enhances the performance of ceria for water splitting'. Together they form a unique fingerprint.

Cite this