Significantly Accelerated Photochemical Perfluorooctanoic Acid Decomposition at the Air–Water Interface of Microdroplets

The efficient elimination of per- and polyfluoroalkyl substances (PFASs) from the environment remains a huge challenge and requires advanced technologies. Herein, we demonstrate that perfluorooctanoic acid (PFOA) photochemical decomposition could be significantly accelerated by simply carrying out this process in microdroplets. The almost complete removal of 100 and 500 μg/L PFOA was observed after 20 min of irradiation in microdroplets, while this was achieved after about 2 h in the corresponding bulk phase counterpart. To better compare the defluorination ratio, 10 mg/L PFOA was used typically, and the defluorination rates in microdroplets were tens of times faster than that in the bulk phase reaction system. The high performances in actual water matrices, universality, and scale-up applicability were demonstrated as well. We revealed in-depth that the great acceleration is due to the abundance of the air–water interface in microdroplets, where the reactants concentration enrichment, ultrahigh interfacial electric field, and partial solvation effects synergistically promoted photoreactions responsible for PFOA decomposition, as evidenced by simulated Raman scattering microscopy imaging, vibrational Stark effect measurement, and DFT calculation. This study provides an effective approach and highlights the important roles of air-water interface of microdroplets in PFASs treatment.