Details

Autor(en) / Beteiligte

• Palmisano, Giovanni
• Scandura, Gabriele
• Augugliaro, Vincenzo
• Loddo, Vittorio
• Pace, Andrea
• Tek, Bilge Sina
• Yurdakal, Sedat
• Palmisano, Leonardo

Titel

Unexpectedly ambivalent O2 role in the autocatalytic photooxidation of 2-methoxybenzyl alcohol in water

Ist Teil von

• Journal of molecular catalysis. A, Chemical, 2015-07, Vol.403, p.37-42

Ort / Verlag

Elsevier B.V

Erscheinungsjahr

2015

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• [Display omitted] •2-Methoxybenzaldehyde could be used as a molecular photocatalyst.•The autocatalytic photooxidation of 4-metoxybenzyl alcohol was investigated.•Double role of molecular oxygen in MBA oxidation and MBAD excited state quencher. An unusual autocatalytic photooxidation of 2-methoxybenzyl alcohol has been observed under UV irradiation in aqueous medium. The homogeneous oxidation is catalyzed by the corresponding aldehyde that is also the main oxidation product. The trend of alcohol disappearance rate matches the typical shape of an autocatalytic process, where a crucial and ambivalent role is played by the presence of molecular oxygen. Low oxygen concentrations give rise to a zero-order reaction since the beginning of irradiation, while higher amounts of oxygen reduce the alcohol oxidation rate until the aldehyde reaches a concentration high enough to speed up the alcohol’s conversion. Experiments performed by varying alcohol, aldehyde and oxygen concentrations in both aqueous and organic media suggest that the alcohol oxidation is initially favored by the presence of oxygen. Once the formed aldehyde competes for photon absorption, the oxidation is driven by aldehydes alpha cleavage leading to reactive oxygenated species in aqueous medium. An excess of oxygen quenches the latter processes thus inhibiting/slowing down the reaction.