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The major EPFRs on the catalysts were formed with g values in the range of 2.0040 to 2.0049, which were phenoxy radicals and semiquinone occurred with higher g value of 2.0075 when the temperature increased to 550 °C, and more EPFRs were produced with the temperature increasing. The addition of iron oxides reduced the spins concentrations of oxygen-centered radicals but increase the spins concentrations of signals with lower g values. The different possible formation pathways of PCDD and PCDF from 1,2,3-TrCBz over metal oxide surface were also propo