Effect of surface modification on back electron transfer dynamics of dibromo fluorescein sensitized TiO₂ nanoparticles

Abstract

Electron injection and back electron transfer (BET) dynamics have been carried out for dibromo fluorescein (DBF) sensitized TiO₂ nanoparticles capped (modified) with sodium dodecyl benzene sulfonate using transient absorption techniques in picosecond and microsecond time domain. BET dynamics have been compared with bare (unmodified) nanoparticles for the same DBF/TiO₂ system. It has been observed that BET reaction is slow on the modified surface compared to a bare surface in earlier time domain (picosecond). This observation has been explained by the fact that on surface modification the energy levels of the semiconductor nanoparticles are pushed up in energy. As a result, the free energy of reaction (−ΔG°) for BET reaction of a dye/SM-TiO₂ system increases as compared to the dye/bare TiO₂ system. High exoergic BET reaction in dye-sensitized TiO₂ nanoparticles surfaces fall in the Marcus inverted regime, so with increasing free energy of reaction, BET rate decreases on the modified surface. However, a reversible trend in BET dynamics has been observed for the above systems in the longer time domain (microsecond). In microsecond time domain BET reaction is faster on the modified surface as compared to on the bare surface. Modification of this surface reduces the density of deep trap states. Recombination dynamics between deep-trapped electron and parent cation is slow due to low coupling strength of BET reaction. As the density of deep-trapped electrons is high in bare particles, BET reaction is slow in longer time domain.