Controllable Syntheses, Crystal Structure Evolution, and Photoluminescence of Polymorphic Zirconium Oxyfluorides

Precise synthesis of polymorphic phases with similar components but distinct crystal structures is one of the key problems in inorganic chemistry. In this work, we report a fluorination method adopting ZrO₂ as the starting material and NH₄F as the fluoridation agent that can afford multiphases in the Zr-O-F system, including Zr₇O₉F₁₀, Zr₃O₂F₈, ZrO_0.46F_3.08, ZrO_0.33F_3.33, β-ZrF₄, NH₄Zr₂F₉, and NH₄ZrF₅. A preliminary phase formation diagram was established as a function of the fluorination temperature (T), reaction time (t), and F/Zr ratio after systematic optimization of the preparation conditions. Among the as-obtained phases, the detailed crystal structures of Zr₇O₉F₁₀ and ZrO_0.33F_3.33 were refined based on the powder X-ray diffraction patterns. As the F/O ratio increases, the crystal structures of Zr-O-F phases transform gradually from an anion-deficient α-UO₃-related structure of Zr₇O₉F₁₀ to an anion-excess ReO₃-related structure of ZrO_0.33F_3.33. At last, we also prepared Ti-doped ZrO₂, Zr₇O₉F₁₀, ZrO_0.46F_3.08, and ZrO_0.33F_3.33 to study the host-lattice-dependent photoluminescence properties of zirconium oxyfluorides. The four materials show distinct photoluminescence in the UV and visible regions due to different local coordination environments of Zr/Ti. This work demonstrates the low-temperature fluorination method as an efficient route to phase-selective polymorphic metal oxyfluorides, which can be employed in further structure-property relationship studies.