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

Author

Listed:
  • 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
    Yale Energy Sciences Institute)

  • Chris Wolverton

    (Northwestern University)

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.

Suggested Citation

  • S. Shahab Naghavi & Antoine A. Emery & Heine A. Hansen & Fei Zhou & Vidvuds Ozolins & Chris Wolverton, 2017. "Giant onsite electronic entropy enhances the performance of ceria for water splitting," Nature Communications, Nature, vol. 8(1), pages 1-6, December.
    • Handle: RePEc:nat:natcom:v:8:y:2017:i:1:d:10.1038_s41467-017-00381-2
    DOI: 10.1038/s41467-017-00381-2
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