Ionothermal synthesis of a three-dimensional zinc phosphate with DFT topology using unstable deep-eutectic solvent as template-delivery agent

A three-dimensional zinc phosphate compound with DFT topology, designated as ZnPO₄-EU1, has been synthesized by an ionothermal approach from the system HF-ZnO–P₂O₅-choline chloride-imidazolidone. Ethylenediamine, derived from decomposition of the imidazolidone component of the deep-eutectic solvent (DES) itself, is delivered to the synthesis and serves as an appropriate template for ZnPO₄-EU1. Experiments in which the synthesis conditions were varied showed that ZnPO₄-EU1 may be prepared over a wide molar ratio of P/Zn = 0.55–13.0. Powder X-ray diffraction patterns have been obtained at intervals to track the crystallization process of this material. The experimental data show that Zn₃(PO₄)₂ · 4H₂O (a dense phase) was first isolated from the DES after reaction for 1 h. Subsequently, the pure phase of ZnPO₄-EU1 was obtained with increasing crystallization time from 12 h to 72 h. The experimental results show that the nucleation and crystallization take place with relatively low levels of solvent degradation, demonstrating that zinc phosphate with a three-dimensional framework can be synthesized by in situ generation of an appropriate template using an unstable DES at high temperatures (150–200 °C).