EPR Evidence for Mechanistic Diversity of Cu(II)/Peroxygen Oxidation Systems by Tracing the Origin of DMPO Spin Adducts

Electron paramagnetic resonance (EPR) has been extensively used for the identification of free radicals that are generated from advanced oxidation processes (AOPs) so as to establish the reaction mechanism. However, some misinterpretations or controversies on the identity of detected EPR signals remain in the literature. This study, with Cu(II)-based AOPs as examples, comprehensively investigated the origin of 5,5-dimethyl-l-pyrroline N-oxide (DMPO) adducts in Cu(II) alone, Cu(II)/H₂O₂, Cu(II)/peroxymonosulfate (PMS), and Cu(II)/peroxydisulfate (PDS) systems. In most Cu(II) systems, DMPO-OH signals can be detected even without any peroxygens, indicating the presence of other origins of this adduct in addition to the genuine spin trapping of ^•OH by DMPO. According to the formed secondary radical adducts (DMPO-OCH₃ from a nonradical process or DMPO-CH₂OH from a radical oxidation) derived from methanol quenching, we propose that CuO⁺, instead of free radicals, is involved in the Cu(II)/PMS system, while ^•OH is indeed generated in the Cu(II)/H₂O₂ and Cu(II)/PDS systems under neutral conditions. Notably, ¹⁷O-incorporation experiments demonstrate that -OH in the detected DMPO-OH adduct originates 100% from water in the Cu(II) alone system but the amount of -OH is over 99.8% from the oxidant while peroxygens are added. In addition, DMPO-O₂^- appears only in the Cu(II)/PDS system under highly alkaline conditions and H₂O is not involved in superoxide formation.