Undiscovered Spin Trapping Artifacts in Persulfate Oxidation Processes: Implications for Identification of Hydroxyl or Sulfate Radicals in Water
Lingli Wang, Qingchao Li, Yu Fu, Zhaohui Wang, Huaiyong Zhu, Mika Sillanpää
Abstract
Electron paramagnetic resonance (EPR) coupled with the spin trapping technique is widely used to identify radicals and has become a tool that is being heavily relied on to probe the reaction mechanism in advanced oxidation processes (AOPs). However, the unexpected spin trapping artifacts in a highly oxidizing environment may mislead the mechanistic interpretations of AOPs. Here, we report previously unrevealed reactions between peroxydisulfate (PDS) and 5,5-dimethyl-1-pyrroline N -oxide (DMPO) or N-tert -butyl-α-phenylnitrone (PBN). The mainly detectable adducts are attributed to DMPO-OH and PBN-OH. Through radical quenching experiments, the nonradical generation pathways of DMPO-OH and PBN-OH are validated, and the 17 O incorporation experiment demonstrates that H 2 O plays a critical role in DMPO-OH production. The formation routes of the primary artifact signals (DMPO-OH, DMPO-SO 4, PBN-OH, and PBN-SO 4 ) are further proposed by applying diverse solvents. PDS may directly oxidize DMPO to generate DMPO-SO 4 in acetonitrile or acetone solvent, while DMPO-OH is yielded using H 2 O as the solvent. The generation of PBN-OH or PBN-SO 4 follows the inverted spin trapping mechanism (a combination of one-electron oxidation and nucleophilic addition). These findings manifest the necessity of selecting the proper spin traps and performing careful control tests during exploration of the catalytic oxidation mechanism under highly oxidizing conditions.