The Use of a Vanadium Species As a Catalyst in Photoinduced Water Oxidation

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• 作者：Marie-Pierre Santoni ; Giuseppina La Ganga ; Viviana Mollica Nardo ; Mirco Natali ; Fausto Puntoriero ; Franco Scandola ; Sebastiano Campagna
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：June 11, 2014
• 年：2014
• 卷：136
• 期：23
• 页码：8189-8192
• 全文大小：263K
• 年卷期：v.136,no.23(June 11, 2014)
• ISSN：1520-5126

文摘

The first water oxidation catalyst containing only vanadium atoms as metal centers is reported. The compound is the mixed-valence [(V^IV₅V^V₁)O₇(OCH₃)₁₂]^{鈭?/sup> species, 1. Photoinduced water oxidation catalyzed by 1, in the presence of Ru(bpy)₃2+ (bpy = 2,2鈥?bipyridine) and Na₂S₂O₈, in acetonitrile/aqueous phosphate buffer takes place with a quantum yield of 0.20. A hole scavenging reaction between the photochemically generated Ru(bpy)₃3+ and 1 occurs with a bimolecular rate constant of 2.5 脳 108 M鈥? s鈥?. The time-resolved formation of the oxidized molecular catalyst 1+ in bimolecular reactions is also evidenced for the first time by transient absorption spectroscopy. This result opens the way to the use of less expensive vanadium clusters as water oxidation catalysts in artificial photosynthesis schemes.}