Dye-sensitized photocatalytic hydrogen generation is emerging as a promising process to produce fuels using a clean and abundant energy source such as sunlight. In the first part of this work, three organic dyes featuring a dithieno[3,2-b:2′,3′-d]silole heterocyclic unit (OB1–OB3), bearing different substituents on various parts of the molecular scaffold, were synthesized, characterized, and used as sensitizers for the commercially available benchmark TiO2 (P25), first in dye-sensitized solar cells and then for the photocatalyzed production of hydrogen with triethanolamine as a sacrificial electron donor. In the second part of the study, aiming to improve the efficiency of the photocatalytic system, P25 was replaced with the less investigated brookite TiO2 polymorph. The photocatalyst obtained upon sensitization with the best performing dye, OB2, still in the presence of Pt as co-catalyst, displayed an enhanced performance in hydrogen production compared to that based on P25 at a lower dye loading. Extended time experiments confirmed that the catalyst was still significantly active after 1 week under continuous illumination, providing a maximum TON of 4201. The higher efficiency of the brookite-based catalytic system and its prolonged stability are especially significant in the perspective of the practical application of the dye-sensitized photocatalytic H2 production technology.
