Tetrathiafulvalene Scaffold-Based Sensitizer on Hierarchical Porous TiO2: Efficient Light-Harvesting Material for Hydrogen Production

Abstract

In this work, a photochemical device that contains thioalkyl-substituted tetrathiafulvalene dyes and hierarchical porous TiO2 has been designed and successfully employed in visible light-driven hydrogen production. The design strategy boosts up the desirable photophysical properties of catalysts and is well supported by optical, electrochemical, and computational studies. The introduction of thioalkyl-substituted tetrathiafulvalene dyes as light-harvesting sensitizers onto the porous TiO2 triggers unprecedented high rate of hydrogen evolution. This study focuses on the role of thiafulvalene scaffold, which can promote ultrafast interfacial electron injection from excited-state dye into the hierarchical porous TiO2 conduction band. The purposeful construction of this integrated composite G3T3 (dye content 1.0 μmol in 10 mg Pt-TiO2 composite) significantly increases the hydrogen production rate of 24 560 μmol h–1 gcat–1 with high apparent quantum yield ∼41%. In the study, the absorption onset of both sensit...