Generation and persistency of combustion-derived environmentally persistent free radicals from phenolic compounds over a Fe2O3/SiO2 surface

Abstract

Combustion of organic solid wastes releases phenolic compounds which can act as precursors in the formation of environmentally persistent free radicals (EPFRs) in the post-flame, cooling zone of waste combustion. The study investigated the generation mechanism of EPFRs from phenolic compounds catalyzed by transition metals in air atmosphere under simulated combustion conditions. Representative combustion-derived phenolic compounds were used, and SiO2 particulates containing different mass ratio of Fe2O3 were synthesized as carriers. EPFRs formed had g-factors between 1.9998 and 2.0066, indicating phenoxyl-, cyclopentadienyl-, and semiquinone-type radicals, along with paramagnetic F-centers. The promotion effect of phenolic compounds on EPFR formation during heating decreased as catechol > hydroquinone > phenol > p-cresol. This trend is related to hydroxyl groups and activation energy. In particular, catechol chemically adsorbed on Fe2O3 at 600 K led to the formation of EPFRs with relatively high spin concentrations (up to 1.28 × 1017 spin/g). Higher Fe2O3 concentrations promoted the transformation of phenoxyl-type radicals into cyclopentadienyl-type and paramagnetic F-centers. However, as the Fe2O3 loading increased from 1.25% to 5%, the density of EPFRs decreased. The findings related to the influence of various precursors and Fe2O3 concentration on EPFR formation provide valuable insights for estimating EPFR generation and associated risk during combustion processes.