Construction of a MIL-101-DGA (MOF) Coupling Betaine Hydrochloride System for the Green and Efficient Separation of Zirconium and Hafnium.

Metal-organic framework materials (MOFs) have potential for practical applications in solid-phase separation technology. However, no studies of the separation of hafnium and zirconium using MOFs have been performed. This work synthesized MIL-101-DGA solid-phase adsorbent material, which was synthesized using amino-containing MIL-101-NH2 as a matrix material by introducing diglycolic acid (DGA) functional groups through a one-step ring-opening reaction. Betaine hydrochloride was selected as the complexing agent to establish the MIL-101-DGA coupling betaine hydrochloride push-pull system; this system could act as an alternative to the traditional MIBK-HSCN separation system. We are the first to report that this MIL-101-DGA coupling betaine hydrochloride system could obtain separation coefficients (βZr/Hf) of 19.7 at pH 0.50 and 8.2 at pH 1.46. Furthermore, the highest adsorption capacity of MIL-101-DGA for Zr was 63.7 mg/g. These results demonstrated that MIL-101-DGA had excellent separation performance for zirconium and hafnium in the betaine hydrochloride medium. This system also exhibited an outstanding cycling performance and immersion stability. After multiple adsorption/desorption cycles and 1 week of immersion in various solutions, the structure and adsorption capability essentially remained unchanged. The adsorption mechanism was thoroughly examined using a suite of analysis and detection methods, including the slope method, FT-IR, XPS, and DFT. In conclusion, we propose that the MIL-101-DGA coupling betaine hydrochloride system, which is an efficient and green separation system, could replace the traditional MIBK-HSCN separation system; our study provides a concept for the industrialization of zirconium and hafnium separation from key mineral resources.