Enhanced Photocatalytic Alcohol Oxidation at the Interface of RuC-Coated TiO₂ Nanorod Arrays

Visible-light-driven organic oxidations carried out under mild conditions offer a sustainable approach to performing chemical transformations important to the chemical industry. This work reports an efficient photocatalytic benzyl alcohol oxidation process using one-dimensional (1D) TiO₂ nanorod (NR)-based photoanodes with surface-adsorbed ruthenium polypyridyl photocatalysts at room temperature. The photocatalyst bis(2,2'-bipyridine)(4,4'-dicarboxy-2,2'-bipyridine)Ru(II) (RuC) was covalently anchored onto TiO₂ nanorod arrays grown on fluorine-doped tin oxide (FTO) electrode surfaces (FTO|t-TiO₂|RuC, t = the thickness of TiO₂ NR). Under aerobic conditions, the photophysical and photocatalytic properties of FTO|t-TiO₂|RuC (t = 1, 2, or 3.5 μm) photoanodes were investigated in a solution containing a hydrogen atom transfer mediator (4-acetamido-2,2,6,6-tetramethylpiperidine-N-oxyl, ACT) as cocatalyst. Dye-sensitized photoelectrochemical cells (DSPECs) using the FTO|t-TiO₂|RuC (t = 1, 2, or 3.5 μm) photoanodes and ACT-containing electrolyte were investigated for carrying out photocatalytic oxidation of a lignin model compound containing a benzylic alcohol functional group. The best-performing anode surface, FTO|1-TiO₂|RuC (shortest NR length), oxidized the 2° alcohol of the lignin model compound to the C_α-ketone form with a > 99% yield over a 4 h photocatalytic experiment with a Faradaic efficiency of 88%. The length of TiO₂ NR arrays (TiO₂ NRAs) on the FTO substrate influenced the photocatalytic performance with longer NRAs underperforming compared to the shorter arrays. The influence of the NR length is hypothesized to affect the homogeneity of the RuC coating and accessibility of the ACT mediator to the RuC-coated TiO₂ surface. The efficient photocatalytic alcohol oxidation with visible light at room temperature as demonstrated in this study is important to the development of sustainable approaches for lignin depolymerization and biomass conversion.