VUV photolysis presents a simple process for VOCs degradation, while the poor mineralization rate and extensive by-products greatly limit its application. In this study, the contribution and synergy between •OH and •O to toluene degradation in the VUV-based process were comprehensively investigated by controlling water and oxygen in the gas flow. It was found that •OH promoted the initial degradation of toluene and macromolecular intermediates, while •O dominated toluene mineralization by boosting the formation of small molecules and CO. Compared with the •OH-dominated VUV photolysis, the presence of catalyst greatly changed the degradation pathway, promoted toluene mineralization into CO and reduced health toxicity via promoting •O formation. This study originally focuses on the key role of •O in VOCs deep oxidation and provides an effective strategy to boost its clean mineralization via the VUV-based process.
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