Heterogeneous photocatayltic deperoxidation with UV and visible light
نویسندگان
چکیده
J Phys Org Chem. 2018;e3807. https://doi.org/10.1002/poc.3807 Abstract A physical‐organic study is described on the photodecomposition of dicumyl peroxide co‐adsorbed with the sensitizers 4,4′‐dimethylbenzil or chlorin e6 on fumed (nonporous) silica. Dicumyl peroxide was decomposed by the heterogeneous photosensitization and monitored by the desorption of products acetophenone, 2‐phenylpropan‐2‐ol, and α‐methylstyrene using proton nuclear magnetic resonance and gas chromatography‐mass spectrometry. Dicumyl peroxide and sensitizer were co‐adsorbed on silica in 1:4 up to 200:1 ratios, with high peroxide destabilization occurring in ratios of about 10:1. This increased photodecomposition corresponded to sensitizer‐peroxide distances of 6 to 9 Å. A Dexter triplet energy transfer mechanism is proposed that explains the short sensitizer and peroxide separation distances for higher peroxide O―O bond homolysis efficiencies on silica. This biphasic (gas/solid) system can thus serve both to destabilize and stabilize a peroxide, which may be of practical use for the delivery of alkoxy radicals for bacterial disinfection.
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