title: Photocatalysis with CdSe nanoparticles in confined media: mapping charge transfer events in the subpicosecond to second timescales.
abstract: Photoinduced charge transfer events between 3 nm diameter CdSe semiconductor nanocrystals and an electron acceptor, MV2+, have been probed in the subpicosecond-microseconds-seconds time scale by confining the reactants in an AOT/heptane reverse micelle. The probe molecule, methyl viologen (MV2+) interacts with the excited CdSe nanoparticle and quenches its emission effectively. The ultrafast electron transfer to MV2+, as monitored from the exciton bleaching recovery of CdSe and the formation of MV+* radical, is completed with an average rate constant of 2.25x10(10) s(-1). Under steady state irradiation (450 nm) the accumulation of MV+* is seen with a net quantum yield of 0.1. Mediation of the electron transfer through TiO2 nanoparticles is achieved by coupling them with the CdSe-MV2+ system within the reverse micelle. This coupling of two semiconductor nanoparticles increases the quantum yield of MV2+ reduction by a factor of 2. The dual roles of TiO2 as an electron shuttle and a rectifier are elucidated by transient absorption spectroscopy and steady state photolysis. The presence of both TiO2 and MV2+ in the reverse micelle creates a synergistic effect to enhance the electron transfer rate constant by an order of magnitude. The time-resolved events that dictate the production and stabilization of electron transfer product provide an insight into the photocatalytic systems that are potentially important in solar hydrogen production and photocatalytic remediation.
authors.affiliation: Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, USA.
authors.forename: Clifton
authors.initials: C
authors.lastname: Harris
authors.forename: Prashant V
authors.initials: PV
authors.lastname: Kamat