Accurate identification of radicals by in-situ electron paramagnetic resonance in ultraviolet-based homogenous...

Accurate identification of radicals in advanced oxidation processes (AOPs) is important to study the mechanisms on radical production and subsequent oxidation-reduction reaction. The commonly applied radical quenching experiments cannot provide direct evidences on generation and evolution of radicals in AOPs, while electron paramagnetic resonance (EPR) is a cutting-edge technology to identify radicals based on spectral characteristics. However, the complexity of EPR spectrum brings uncertainty and inconsistency to radical identification and mechanism clarification. This work presented a comprehensive study on identification of radicals by in-situ EPR analysis in four typical UV-based homogenous AOPs, including UV/H₂O₂, UV/peroxodisulfate (and peroxymonosulfate), UV/peracetic acid and UV/IO₄^- systems. Radical formation mechanism was also clarified based on EPR results. A reliable EPR method using organic solvents was proposed to identify alkoxy and alkyl radicals (CH₃C(=O)OO·, CH₃C(=O)O· and ·CH₃) in UV/PAA system. Two activation pathways for radical production were proposed in UV/IO₄^- system, in which the produced IO₃·, IO₄·, ·OH and hydrated electron were precisely detected. It is interesting that addition of specific organic solvents can effectively identify oxygen-center and carbon-center radicals. A key parameter in EPR spectrum for 5,5-dimethyl-1-pyrroline N-oxide (DMPO) spin adduct, A_H, is ranked as: ·CH₃ (23 G) >·OH (15 G) >IO₃· (12.9 G) >O₂·^- (11 G) ≥·OOH (9-11 G) ≥IO₄· (9-10 G) ≥SO₄·^- (9-10 G) >CH₃C(=O)OO· (8.5 G) > CH₃C(=O)O· (7.5 G). This study will give a systematic method on identification of radicals in AOPs, and shed light on the insightful understanding of radical production mechanism.