Department of Chemistry, University of Washington, Box 351700, Seattle, Washington 98195-1700, United States.
J Am Chem Soc. 2022 Aug 10;144(31):14226-14234. doi: 10.1021/jacs.2c04991. Epub 2022 Jul 27.
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 ' 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, 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.
测量和调节量子点界面的电荷转移过程是将量子点开发为光催化剂的关键步骤。在这项工作中,通过直接探测包括空穴和电子受体在内的分子电荷受体库的氧化态变化,证明了在光照下进行循环伏安法可测量从 CdS 量子点光诱导电荷转移的速率。伏安法数据表明,量子点的本征光掺杂产生了长寿命的电荷给体态,以及驱动力和电荷转移速率之间存在正相关关系。光照下的伏安图变化遵循“能带图”的机理预测,电化学建模允许测量有效的电子转移速率。光诱导电荷转移的观察速率约为 0.1 s,与传统瞬态光学光谱法测量的皮秒动力学明显不同,并且与光介导的化学转化的量子产率更紧密相关。