Synthesis, Structure, and Selective Gas Adsorption of a Single-Crystalline Zirconium Based Microporous Metal–Organic Framework

Porous metal–organic framework (MOF) materials with high thermal and water stability are desirable for various adsorption based applications. Early transition metal based MOFs such as those built on zirconium metal have been well recognized for their excellent stability toward heat and/or moisture. However, the difficulty growing large single crystals makes their structural characterization challenging. Herein we report a porous Zr-MOF, [Zr₆O₄(OH)₄(cca)₆] (Zr-cca), which is assembled from zirconium and 4-carboxycinnamic acid (H₂cca) under solvothermal conditions. Single crystal X-ray diffraction analysis reveals that the structure of Zr-cca is isoreticular to the prototype zirconium based MOF, UiO-66. Zr-cca shows permanent porosity upon removal of solvent molecules initially residing inside the pores, with a BET surface area of 1178 m²/g. As expected, it exhibits good thermal stability (stable up to 400 °C) and high resistance to acidity over a wide pH range. Evaluation of its gas adsorption performance on various hydrocarbons and fluorocarbons indicates that it preferentially adsorbs C₃ and C₄ hydrocarbons over C₂ analogues. At 30 °C Zr-cca takes up more than 50 wt % of perfluorohexane and the adsorption–desorption process is fully recyclable. We have compared this material with UiO-66 and studied the underlying reasons for the difference in their adsorption performance toward perfluorohexane