Visible light induced degradation of perfluorooctanoic acid using iodine deficient bismuth oxyiodide photocatalyst

A bismuth oxyiodide photocatalyst having coexistent iodine deficient phases viz. Bi₄O₅I₂ and Bi₅O₇I was prepared by using a solvothermal method followed by calcination process. This has been used for the degradation of model perfluoroalkyl acids such as perfluorooctanoic acid at low concentrations (1 ppm) under simulated solar light irradiation. 94% PFOA degradation with a rate constant of 1.7 h^-1 and 65% defluorination of PFOA have been achieved following 2 h of photocatalysis. The degradation of PFOA happened by the parallel direct redox reactions with high energy photoexcited electrons at the conduction band, electrons in iodine vacancies and superoxide radicals. The degradation intermediates were analyzed by electrospray ionization-mass spectrometry in the negative mode. The catalyst was converted to a more iodine deficient Bi₅O₇I phase during photocatalysis following creation of iodine vacancies, some of which were compensated by the fluoride ions released from degraded PFOA.