Preparation-Dependent Composition and O/F Ordering in NbO₂F and TaO₂F

Through an analysis combining powder XRD, TGA, and ¹⁹F and ¹H solid-state NMR, it is confirmed for NbO₂F and shown for TaO₂F that both contain hydroxyl defects and metal vacancies when prepared by aqueous solution synthesis. The formulations M_1-x□_xO_2-5x(OH,F)_1+5x of both the samples are determined. The effects of the usually applied thermal treatments are examined. Obtaining pure NbO₂F and TaO₂F from these samples, that is, fully removing metal vacancies and hydroxide, while avoiding the formation of M₂O₅, is not that easy. Since thermal treatments result in dehydroxylation and defluorination, it requires, at least, a larger amount of fluorine than metal initially, which may not be the case. We also confirm that the solid-state synthesis is an efficient method to avoid metal vacancies and hydroxyl defects in NbO₂F and then apply it to the synthesis of TaO₂F. The local structure of NbO₂F and TaO₂F is poorly described by an ideal cubic ReO₃-type model with O and F randomly distributed over the available anion sites. Since O/F ordering was previously highlighted, NbO₂F and TaO₂F cubic 3 × 3 × 3 supercells featuring -M-O-M-O-M-F- chains along ⟨100⟩ have been built and geometry optimized. These optimized supercells lead to more realistic structures than the previously proposed models, that is, really disordered structures with angularly and radially distorted MX₆ octahedra as expected in disordered compounds. Moreover, the structural modeling of NbO₂F and TaO₂F by these geometry-optimized supercells is supported by the computed ¹⁹F and ⁹³Nb NMR parameters, which give very good agreement with the experimental ones.