Photoinduced Charge Transfer from Quantum Dots Measured by Cyclic Voltammetry

Measuring and modulating charge-transfer processes at quantum dot interfaces are crucial steps in developing quantum dots as photocatalysts. In this work, cyclic voltammetry under illumination is demonstrated to measure the rate of photoinduced charge transfer from CdS quantum dots by directly probing the changing oxidation states of a library of molecular charge acceptors, including both hole and electron acceptors. The voltammetry data demonstrate the presence of long-lived charge donor states generated by native photodoping of the quantum dots as well as a positive correlation between driving force and rate of charge transfer. Changes to the voltammograms under illumination follow mechanistic predictions from the E_rC_i' zone diagram, and electrochemical modeling allows for measurement of the rate of productive electron transfer. Observed rates for photoinduced charge transfer are on the order of 0.1 s^-1, which are distinct from the picosecond dynamics measured by conventional transient optical spectroscopy methods and are more closely connected to the quantum yield of light-mediated chemical transformations.