Oxygen Vacancy Distribution in Yttrium-Doped Ceria from (89)Y–(89)Y Correlations via Dynamic Nuclear Polarization Solid-State NMR

[Image: see text] Comprehending the oxygen vacancy distribution in oxide ion conductors requires structural insights over various length scales: from the local coordination preferences to the possible formation of agglomerates comprising a large number of vacancies. In Y-doped ceria, (89)Y NMR enables differentiation of yttrium sites by quantification of the oxygen vacancies in their first coordination sphere. Because of the extremely low sensitivity of (89)Y, longer-range information was so far not available from NMR. Herein, we utilize metal ion-based dynamic nuclear polarization, where polarization from Gd(III) dopants provides large sensitivity enhancements homogeneously throughout the bulk of the sample. This enables following (89)Y–(89)Y homonuclear dipolar correlations and probing the local distribution of yttrium sites, which show no evidence of the formation of oxygen vacancy rich regions. The presented approach can provide valuable structural insights for designing oxide ion conductors.