Can the commonly used quenching method really evaluate the role of reactive oxygen species in pollutant abatement during catalytic ozonation?

Reactive oxygen species (ROS) such as hydroxyl radicals (•OH), superoxide radicals (O2•-), and singlet oxygen (1O2) have often been suggested to play a role in ozone-resistant pollutant abatement during catalytic ozonation. However, there are significant controversies regarding their relative importance in literature. Currently, the role of ROS in pollutant abatement is commonly evaluated by the quenching method based on the assumption that the added ROS quenchers (e.g., tert-butanol (TBA) and para-benzoquinone (pBQ)) quench only the target ROS, but do not considerably influence other reaction mechanisms of catalytic ozonation. However, we hypothesized that this assumption is possibly unrealistic and a main cause for the controversies reported in literature. To test this hypothesis, this study evaluated the effects of six commonly used ROS quenchers (TBA, pBQ, methanol (MeOH), 4-chloro-7-nitrobenzo-2-oxa-1,3-dizole (NBD-Cl), furfuryl alcohol (FFA), and sodium azide (NaN3)) on the mechanism of catalytic ozonation with manganese dioxide. The results show that rather than only quenching their target ROS, these quenchers can profoundly change the catalytic ozonation system through various mechanisms, e.g., interrupting the radical chain reaction of O3 decomposition, blocking the active sites of catalysts, and consuming O3 in the system. Due to the significant confounding effects of ROS quenchers on the reaction mechanism, the quenching method actually cannot reveal the role of ROS in pollutant abatement and often misinterpreted the catalytic ozonation mechanism. The results indicate that the commonly used quenching method is probably not an appropriate way to investigate the role of ROS in pollutant abatement during catalytic ozonation, and many previously reported mechanisms obtained with the quenching method may need a revisit.