(17)O solid-state NMR spectroscopy of A(2)B(2)O(7) oxides: quantitative isotopic enrichment and spectral acquisition?

The potential of (17)O NMR spectroscopy for the investigation of A(2)B(2)O(7) ceramic oxides important in the encapsulation of radioactive waste is demonstrated, with post-synthetic enrichment by exchange with (17)O(2) gas. For Y(2)Sn(2)O(7), Y(2)Ti(2)O(7) and La(2)Sn(2)O(7) pyrochlores, enrichment of the two distinct O species is clearly non quantitative at lower temperatures (∼700 °C and below) and at shorter times, despite these being used in prior work, with preferential enrichment of OA(2)B(2) favoured over that of OA(4). At higher temperatures, the (17)O NMR spectra suggest that quantitative enrichment has been achieved, but the integrated signal intensities do not reflect the crystallographic 1 : 6 (O1 : O2) ratio until corrected for differences in T(1) relaxation rates and, more importantly, the contribution of the satellite transitions. (17)O NMR spectra of Y(2)Zr(2)O(7) and Y(2)Hf(2)O(7) defect fluorites showed little difference with any variation in enrichment temperature or time, although an increase in the absolute level of enrichment (up to ∼7.5%) was observed at higher temperature. DFT calculations show that the six distinct resonances observed cannot be assigned unambiguously, as each has contributions from more than one of the five possible next nearest neighbour environments. For La(2)Ti(2)O(7), which adopts a layered perovskite-like structure, little difference in the spectral intensities is observed with enrichment time or temperature, although the highest absolute levels of enrichment (∼13%) were obtained at higher temperature. This work demonstrates that (17)O NMR has the potential to be a powerful probe of local structure and disorder in oxides, but that considerable care must be taken both in choosing the conditions for (17)O enrichment and the experimental acquisition parameters if the necessary quantitative measurements are to be obtained for more complex systems.