ABSTRACT
On account of its nonbiodegradable nature and persistence in the environment, perfluorooctanoic acid (PFOA) accumulates in water resources and poses serious environmental issues in many parts of the world. Here, we present the development of two fluorine-rich calix[4]arene-based porous polymers, FCX4-P and FCX4-BP, and demonstrate their utility for the efficient removal of PFOA from water. These materials featured Brunauer-Emmett-Teller (BET) surface areas of up to 450 m2 g-1, which is slightly lower than their nonfluorinated counterparts (up to 596 m2 g-1). FCX4-P removes PFOA at environmentally relevant concentrations with a high rate constant of 3.80 g mg-1 h-1 and reached an exceptional maximum PFOA uptake capacity of 188.7 mg g-1. In addition, it could be regenerated by simple methanol wash and reused without a significant decrease in performance.
ABSTRACT
Herein, we report a semiconductive, proton-conductive, microporous hydrogen-bonded organic framework (HOF) derived from phenylphosphonic acid and 5,10,15,20-tetrakis[p-phenylphosphonic acid] porphyrin (GTUB5). The structure of GTUB5 was characterized using single crystal X-ray diffraction. A narrow band gap of 1.56 eV was extracted from a UV-Vis spectrum of pure GTUB5 crystals, in excellent agreement with the 1.65 eV band gap obtained from DFT calculations. The same band gap was also measured for GTUB5 in DMSO. The proton conductivity of GTUB5 was measured to be 3.00 × 10-6 S cm-1 at 75 °C and 75% relative humidity. The surface area was estimated to be 422 m2 g-1 from grand canonical Monte Carlo simulations. XRD showed that GTUB5 is thermally stable under relative humidities of up to 90% at 90 °C. These findings pave the way for a new family of organic, microporous, and semiconducting materials with high surface areas and high thermal stabilities.
