Topochemical Nitridation with Anion Vacancy-Assisted N3–/O2– Exchange

We present how the introduction of anion vacancies in oxyhydrides enables a route to access new oxynitrides, by conducting ammonolysis of perovskite oxyhydride EuTiO3–xHx (x ∼ 0.18). At 400 °C, similar to our studies on BaTiO3–xHx, hydride lability enables a low temperature direct ammonolysis of EuTi3.82+O2.82H0.18, leading to the N3–/H–-exchanged product EuTi4+O2.82N0.12□0.06. When the ammonolysis temperature was increased up to 800 °C, we observed a further nitridation involving N3–/O2– exchange, yielding a fully oxidized Eu3+Ti4+O2N with the GdFeO3-type distortion (Pnma) as a metastable phase, instead of pyrochlore structure. Interestingly, the same reactions using the oxide EuTiO3 proceeded through a 1:1 exchange of N3– with O2– only above 600 °C and resulted in incomplete nitridation to EuTiO2.25N0.75, indicating that anion vacancies created during the initial nitridation process of EuTiO2.82H0.18 play a crucial role in promoting anion (N3–/O2–) exchange at high temperatures. Hence, by using (hydride...