Formation of DF, PCDD/Fs and EPFRs from 1,2,3-trichlorobenzene over metal oxide/silica surface

The formation of dibenzofuran (DF), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and environmentally persistent free radicals (EPFRs) from 1,2,3-trichlorobenzene (1,2,3-TrCBz) over metal oxide / silica surface were investigated using a tubular furnace. PCDD/Fs increased exponentially from 250 to 550 °C over copper oxide / silica surface and PCDD/Fs had the maximum growth from 400 to 450 °C. The ratio of PCDD / PCDF was much less than 1, especially when the temperature raised from 450 to 550 °C. Pentachlorianated dibenzo-p-furan (PeCDF) dominated among the homologues, which contributed 45-61% to the total PCDD/Fs. Two peaks of the yield of DF occurred at 400 °C and 500 °C respectively. Furthermore, the oxygen contents have different effects for PCDD and PCDF formation, and low oxygen could promote PCDD production, especially for tetrachlorinated dibenzo-p-dioxin (TCDD). More PCDF were formed on the oxygen rich condition, indicating that the oxygen promoted the chlorination of DF. Iron oxides are better than copper oxides to catalyze the formation of PCDD/Fs from 1,2,3-TrCBzs at 350 °C, especially for PCDF. 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 proposed.