Rare-earth metal-organic frameworks with their unique optical and electronic properties have gained interest in recent years. Previously, the synthesis of fluoro-bridged RE metal-organic frameworks with the use of fluorinated modulators such as 2-fluorobenzoic acid or 2,6-difluorobenzoic acid have been reported. This research shows the cleavage of the C-F bond of perfluoroalkyl substances with rare-earth ions. Perfluoroalkyl substances (PFAS) as a large, complex, and ever-expanding group of manufactured compounds are used in a wide array of industrial and commercial products to make them more resistant to stains, grease, and water. Because the carbon-fluorine (C-F) bond is among the most chemically robust bonds; the degradation of fluorinated hydrocarbons in the environment is exceptionally difficult. Multiple fluorine atoms from perfluorooctanoic acid (PFOA) and perfluorhexanoic acid (PFHA) can be removed and bridge the lanthanide atoms in the lanthanide fluoride structure. For the first time, RE (Ho3+, Gd3+, Dy3+, Eu3+, Tb3+) fluoro-bridged nonacluster and tricluster of a highly connected known metal-organic framework with perfluorooctanoic acid and perfluorhexanoic acid as modulator have been synthesized. Additionally, the transformation of a 2-FBA dimeric lanthanide complex into the fluoro-bridged nonacluster and tricluster MOF will also be described. Characteristics studies such as single-crystal X-ray diffraction crystallography, powder X-ray diffraction (PXRD), X-Ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), energy-dispersive X-ray spectroscopy (EDS), and fourier-transform infrared spectroscopy (FT-IR) are performed to confirm the synthesis of fluoro-bridged nonacluster and tricluster metal-organic frameworks.

Difluorination of per- and polyfluoroalkyl substances (PFAS) by rare-earth ions and construction of fluoro-bridged metal-organic frameworks

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ACS Fall 2022

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