Nanoscale connectivity in a TiO2/CdSe quantum dots/functionalized graphene oxide nanosheets/Au nanoparticles...

Electron transfer dynamics in a photoactive coating made of CdSe quantum dots (QDs) and Au nanoparticles (NPs) tethered to a framework of ionic liquid functionalized graphene oxide (FGO) nanosheets and mesoporous titania (TiO(2)) was studied. High resolution transmission electron microscopy analyses on TiO(2)/CdSe/FGO/Au not only revealed the linker mediated binding of CdSe QDs with TiO(2) but also, surprisingly, revealed a nanoscale connectivity between CdSe QDs, Au NPs and TiO(2) with FGO nanosheets, achieved by a simple solution processing method. Time resolved fluorescence decay experiments coupled with the systematic quenching of CdSe emission by Au NPs or FGO nanosheets or by a combination of the latter two provide concrete evidences favoring the most likely pathway of ultrafast decay of excited CdSe in the composite to be a relay mechanism. A balance between energetics and kinetics of the system is realized by alignment of conduction band edges, whereby, CdSe QDs inject photogenerated electrons into the conduction band of TiO(2), from where, electrons are promptly transferred to FGO nanosheets and then through Au NPs to the current collector. Conductive-atomic force microscopy also provided a direct correlation between the local nanostructure and the enhanced ability of composite to conduct electrons. Point contact I-V measurements and average photoconductivity results demonstrated the current distribution as well as the population of conducting domains to be uniform across the TiO(2)/CdSe/FGO/Au composite, thus validating the higher photocurrent generation. A six-fold enhancement in photocurrent and a 100 mV increment in photovoltage combined with an incident photon to current conversion efficiency of 27%, achieved in the composite, compared to the inferior performance of the TiO(2)/CdSe/Au composite imply that FGO nanosheets and Au NPs work in tandem to promote charge separation and furnish less impeded pathways for electron transfer and transport. Such a hierarchical rapid electron transfer model can be adapted to other nanostructures as well, as they can favorably impact photoelectrochemical performance.