Efficient Light-Driven Oxidation of Alcohols Using an Organic Chromophore–Catalyst Assembly Anchored to TiO2

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• 作者：Toan V. Pho ; Matthew V. Sheridan ; Zachary A. Morseth ; Benjamin D. Sherman ; Thomas J. Meyer ; John M. Papanikolas ; Kirk S. Schanze ; John R. Reynolds
• 刊名：ACS Applied Materials & Interfaces
• 出版年：2016
• 出版时间：April 13, 2016
• 年：2016
• 卷：8
• 期：14
• 页码：9125-9133
• 全文大小：533K
• 年卷期：0
• ISSN：1944-8252

文摘

The ligand 5-PO₃H₂-2,2′:5′,2″-terthiophene-5-trpy, T3 (trpy = 2,2′:6′,2″-terpyridine), was prepared and studied in aqueous solutions along with its metal complex assembly [Ru(T3)(bpy)(OH₂)]²⁺ (T3-Ru-OH₂, bpy = 2,2′-bipyridine). T3 contains a phosphonic acid group for anchoring to a TiO₂ photoanode under aqueous conditions, a terthiophene fragment for light absorption and electron injection into TiO₂, and a terminal trpy ligand for the construction of assemblies comprising a molecular oxidation catalyst. At a TiO₂ photoanode, T3 displays efficient injection at pH 4.35 as evidenced by the high photocurrents (∼350 uA/cm²) arising from hydroquinone oxidation. Addition of [Ru(bpy)(OTf)][OTf]₂ (bpy = 2,2′-bipyridine, OTf^– = triflate) to T3 at the free trpy ligand forms the molecular assembly, T3-Ru-OH₂, with the oxidative catalyst fragment: [Ru(trpy)(bpy)(OH₂)]²⁺. The new assembly, T3-Ru-OH₂, was used to perform efficient light-driven oxidation of phenol (230 μA/cm²) and benzyl alcohol (25 μA/cm²) in a dye-sensitized photoelectrosynthesis cell.