Direct Photooxidation and Xanthene-Sensitized Oxidation of Naphthols: Quantum Yields and Mechanism
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- 作者：Michael Oelgemo虉ller ; Jochen Mattay ; Helmut Go虉rner
- 刊名：Journal of Physical Chemistry A
- 出版年：2011
- 出版时间：January 27, 2011
- 年：2011
- 卷：115
- 期：3
- 页码：280-285
- 全文大小：244K
- 年卷期：v.115,no.3(January 27, 2011)
- ISSN：1520-5215
文摘
The photoinduced oxidation of 1-naphthol to 1,4-naphthoquinone and of 5-hydroxy-1-naphthol to 5-hydroxy-1,4-naphthoquinone was studied by steady-state and time-resolved techniques. The direct photooxidation of naphthols in methanol or water takes place by reaction of the naphoxyl radical (鈥?/b>ONaph) with the superoxide ion radical (O2鈥?/b>鈭?/sup>), the latter of which results from the reaction of the solvated electron with oxygen after photoionization. The sensitized oxidation takes place by energy transfer from the xanthene triplet state to oxygen. From the two oxygen atoms, which are consumed, one is incorporated into the naphthol molecule giving naphthoquinone and the second gives rise to water. The effects of eosin, erythrosin, and rose bengal in aqueous solution, pH, and the oxygen and naphthol concentrations were studied. The quantum yield of the photosensitized transformation was determined, which increases with the naphthol concentration and is largest at pH > 10. The quantum yield of oxygen uptake is similar. The pathway involving singlet molecular oxygen is suggested to operate for the three sensitizers. The alternative pathway via electron transfer from the naphthol to the xanthene triplet state and subsequent reaction of 鈥?/b>ONaph with O2鈥?/b>鈭?/sup>, the latter of which is formed by scavenging of the xanthene radical anion by oxygen, does also contribute.