Size-controlled interparticle charge transfer between TiO2 and quantized capacitors

COLL 196

Junhyung Kim, jun.h.kim@wmich.edu and Dongil Lee, dongil.lee@wmich.edu. Department of Chemistry, Western Michigan University, 1903 W. Michigan Avenue, 3425 Wood Hall, Kalamazoo, MI 49008
We present the charge transfer quenching of photoexcited TiO2 nanoparticles by hexanethiolate monolayer protected gold clusters (MPCs) with core diameters of 1.1-4.9 nm. The quenching efficiency of Au MPCs was compared using Stern-Volmer plots. The quenching constants (Kq) taken from slopes of the plots reveal that Kq increases from 5.6x105 to 4.09x107 by more than 70-fold as the core diameter increases from 1.1 to 4.9 nm. The origin of the size dependence is considered. Kq was found to linearly correlate with the MPC capacitance. This suggests that the quenching process is dominantly controlled by the capacitance of the electron acceptor (Au MPC). Kq for 1.1 nm diameter Au MPC was found to be significantly smaller than that predicted by the Kq-capacitance correlation. This may reflect the size-dependent opening of an energy gap at the Fermi level for molecule-like MPCs.