Secondary photosensitization reactions can play a role in degradation after an initial photosensitized oxidation produces peroxides initiated by reactive oxygen intermediates (ROIs). These ROIs lead to peroxides, such as ‘ene’ hydroperoxides and endoperoxides. There is evidence that these peroxides to decompose not only thermally, but also by subsequent photosensitization in the homolysis of the peroxide O–O and OO–H bonds, but little mechanistic work has been carried out on the secondary sensitization of peroxides following their primary formation in photosensitized oxidation. The results of a comparative study will be presented by modeling the downstream second illumination in the photosensitized homolysis of cumylethyl peroxide, dicumyl peroxide, di-<i>t</i>-butyl peroxide, and <i>t</i>-butyl hydroperoxide in heterogeneous media (gas/nanoparticle interface) and/or in solution, in which results from previous work of Scaiano et al. will also be drawn on. The radical production will be assessed via the peroxides’ photosensitized homolysis, including alkoxy radical migration and chain termination to the ROOR product, as well as chain propagation processes to extend the oxyradicals’ reach.

Effect of secondary photosensitization on the degradation of initially formed peroxides to extend oxyradicals’ reach

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ACS Fall 2022

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.