摘要： 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 boost up the desirable photophysical properties of the catalysts and well supported from the 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 24560 μmol.h-1g-1 cat with high apparent quantum yield (AQY) ~ 41%. In the study, both sensitizers absorption onset extends up to 500 nm in solution and 600 nm on hierarchical porous TiO2. Density functional theory (DFT) in the present study described that the HOMO levels are delocalized on anthracene as well as tetrathiafulvalene donor units, and LUMO covers on to the carboxylate anchoring group in both dyes. This study unveiled first time that a tetrathiafulvalene scaffolds in porous TiO2 attributes to positive synergistic effects in hydrogen production.