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>Synthesis, Structure, and Selective Gas Adsorption of a Single-Crystalline Zirconium Based Microporous Metal-Organic Framework
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Synthesis, Structure, and Selective Gas Adsorption of a Single-Crystalline Zirconium Based Microporous Metal-Organic Framework
Porous metal organic framework (MOP) 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 (H(2)cca) 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 m(2)/g. As expected, it exhibits good thermal stability (stable up to 400 degrees 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 C-3 and C-4 hydrocarbons over C-2 analogues. At 30 degrees 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.
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