Hydration mechanisms and proton conduction in the mixed ionic–electronic conductors Ba4Nb2O9 and Ba4Ta2O9

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dc.contributor.authorWind, Jen_AU
dc.contributor.authorMole, RAen_AU
dc.contributor.authorYu, DHen_AU
dc.contributor.authorAvdeev, Men_AU
dc.contributor.authorLing, CDen_AU
dc.date.accessioned2021-06-28T00:48:47Zen_AU
dc.date.available2021-06-28T00:48:47Zen_AU
dc.date.issued2018-07-12en_AU
dc.date.statistics2021-06-16en_AU
dc.description.abstractWe studied the behavior of hydrogen in the mixed ionic–electronic conductors γ-Ba4Nb2O9 and 6H-Ba4Ta2O9 using a combination of experimental (neutron diffraction and inelastic neutron scattering) and computational (ab initio molecular dynamics) methods. Although these compounds have isostructural low-temperature polymorphs, they adopt distinct forms in the high-temperature conducting regime. We show here that they also have distinct mechanisms for hydration and ionic conduction. Hydration of γ-Ba4Nb2O9 is localized to 2-D layers in the structure that contain a 1:1 ratio of isolated but adjacent NbO4 and NbO5 polyhedra. OH– and H+ ions combine with two polyhedra, respectively, to form complete layers of NbO4OH polyhedra, giving rise to a stoichiometric hydrated form γ-III-Ba4Nb2O9·1/3H2O. Protons then diffuse through these 2-D layers by “hopping” between oxygen atoms on adjacent polyhedra. In the case of 6H-Ba4Ta2O9, hydration occurs by intercalating intact water molecules into the structure up to a maximum of ∼0.375 H2O per formula unit. This explains the unusual local and long-range structural distortions in the hydrated form observed by neutron diffraction. Diffusion then occurs by water molecules moving between neighboring symmetry equivalent positions. These fundamentally different hydration and proton conduction mechanisms explain why 6H-Ba4Ta2O9 has the less well-defined and higher maximum water content, while γ-Ba4Nb2O9 has the higher proton conductivity. © 2018 American Chemical Societyen_AU
dc.identifier.citationWind, J., Mole, R. A., Yu, D., Avdeev, M., & Ling, C. D. (2018). Hydration mechanisms and proton conduction in the mixed ionic–electronic conductors Ba4Nb2O9 and Ba4Ta2O9. Chemistry of Materials, 30(15), 4949-4958. doi:10.1021/acs.chemmater.8b00950en_AU
dc.identifier.issn1520-5002en_AU
dc.identifier.issue15en_AU
dc.identifier.journaltitleChemistry of Materialsen_AU
dc.identifier.pagination4949-4958en_AU
dc.identifier.urihttps://doi.org/10.1021/acs.chemmater.8b00950en_AU
dc.identifier.urihttps://apo.ansto.gov.au/dspace/handle/10238/10907en_AU
dc.identifier.volume30en_AU
dc.language.isoenen_AU
dc.publisherAmerican Chemical Societyen_AU
dc.subjectOxygenen_AU
dc.subjectEnergyen_AU
dc.subjectMolecular dynamics methoden_AU
dc.subjectHydrationen_AU
dc.subjectNeutron diffractionen_AU
dc.subjectElectric conductorsen_AU
dc.subjectIonic conductivityen_AU
dc.titleHydration mechanisms and proton conduction in the mixed ionic–electronic conductors Ba4Nb2O9 and Ba4Ta2O9en_AU
dc.typeJournal Articleen_AU
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