Ultrafast Charge Separation and Long-Lived Charge Separated State in Photocatalytic CdS-Pt Nanorod Heterostructures

Colloidal semiconductor-metal nanoheterostructures that combine the light-harvesting ability of semiconductor nanocrystals with the catalytic activity of small metal nanoparticles show promising applications for photocatalysis, including light-driven H-2 production. The exciton in the semiconductor domain can be quenched by electron-, hole-, and energy transfer to the metal particle, and the competition between these processes determines the photocatalytic efficiency of these materials. Using ultrafast transient absorption spectroscopy, we show that, in CdS-Pt heterostructures consisting of a CdS nanorod with a Pt nanoparticle at one end, the excitons in the CdS domain dissociate by ultrafast electron transfer (with a half-life of similar to 3.4 ps) to the Pt. The charge separated state is surprisingly long-lived (with a half-life of similar to 1.2 +/- 0.6 mu s) due to the trapping of holes in CdS. The asymmetry in the charge separation and recombination times is believed to be the key feature that enables the accumulation of the transferred electrons in the Pt tip and photocatalysis in the presence of sacrificial hole acceptors.