Insight into degradation mechanism of PCBs from thermal desorption off-gas over iron-based catalysts

Iron-based catalysts were developed to achieve the hydrodechlorination (HDC)/oxidation of polychlorinated biphenyls (PCBs) from thermal desorption off-gas, and Fe₃O₄/γ-Al₂O₃ showed higher dechlorination efficiency than Fe₂O₃/γ-Al₂O₃. The optimal Fe loading resulted in 95.5% degradation efficiency and 76.9% toxicity reduction of gaseous PCBs, and the optimal Fe₃O₄/γ-Al₂O₃ exhibited excellent stability during a 60-h test. The gas chromatography-mass spectrometry analysis of intermediate products indicated the presence of two competitive degradation pathways, namely, hydrodechlorination and oxidation with Fe₃O₄/γ-Al₂O₃ as catalyst. During the first stage (reductive dechlorination), the reductive activity of iron-based catalysts was effectively enhanced in the presence of water, which was confirmed by density functional theory (DFT) calculations. The removal of chlorine atoms was found in the order of meta > para > ortho. During the second stage (oxidation), hydroxyl and superoxide anion radicals were found to attack PCBs on the surface of Fe₃O₄/γ-Al₂O₃. This study provides an insight into the HDC and oxidation mechanism of gaseous PCBs over iron-based catalysts.