Viologens are well-suited for serving as electron-transfer
mediators
in redox systems due to their low reduction potential and ability
to form stable radical cations. Because of this feature, viologens
can play a key role in modifying semiconductors toward enhanced photocatalytic
performance. Herein, a series of hybrid photocatalysts composed of
TiO2 nanoparticles and star-shaped viologen derivatives
with different alkyl chains [TPCBP-X_TiO2; X: ethyl (E),
butyl (B), hexyl (H) and octyl (O)] were prepared for the photocatalytic
hydrogen evolution from water under visible-light irradiation. The
TPCBP-X molecules not only provide photosensitization of TiO2 nanoparticles in the visible-light region but also act as an efficient
electron-transfer mediator for the transfer of photoinduced electrons
to TiO2 and Pt. Among these photocatalysts, TPCBP-E_TiO2 exhibited a 1.013 mmol g–1 h–1 H2 evolution rate with an apparent quantum yield (AQY)
of 20.15% (470 nm), which dramatically improved hydrogen evolution
activity among the other structures [TPCBP-X_TiO2 (X; B,
H, O)] due to the more porous and uniform surface, resulting in its
low barrier effect for electron transfer. In addition, in the presence
of a Pt cocatalyst, TPCBP-E_TiO2 yielded a H2 evolution rate of 17.7 mmol g–1, which is about
2.2 times higher than that of pure TPCBP-E_TiO2 (8.1 mmol
g–1) after 8 h of visible-light illumination.