(Keynote) Photoinduced Charge Transfer from Quantum Dots Measured By Cyclic Voltammetry

Abstract

Measuring and modulating charge transfer processes at quantum dot interfaces are crucial steps in the development of quantum dot photocatalysis. 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 model charge acceptors. The voltammetry data demonstrates the presence of long-lived electron donor states generated by native photodoping of the QDs as well as the relationship between driving force and rate of charge transfer. Changes to the voltammograms under illumination follow mechanistic predictions from classic zone diagrams and electrochemical modeling allows for measurement of the rate of productive electron transfer, giving rate constants (104 M-1s-1) that are distinct from the ps dynamics measured by conventional optical spectroscopy methods and that are more closely connected to the quantum yield of photoinduced chemical transformations.