Ligand dissociation mediated charge transfer observed at colloidal W18O49 nanoparticle interfaces.
Ligand dissociation mediated charge transfer observed at colloidal W18O49 nanoparticle interfaces.
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DOI：
10.1021/la404019v
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发表时间：
2014-02
期刊：
影响因子：
--
通讯作者：
D. Grauer;A. Alivisatos
中科院分区：
文献类型：
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作者：
D. Grauer;A. Alivisatos
通过胶体纳米粒子的配体壳了解电荷转移动力学一直是太阳能转换的重要追求。虽然在静态干燥和电化学系统中已经深入研究了通过纳米颗粒膜的配体壳层的电荷传输，但其对分散胶体系统中电荷转移动力学的影响相对较少受到关注。本工作报告了有机可溶性三-（1，10-菲咯啉）铁（III）衍生物对胺钝化的氧化钨纳米颗粒的氧化作用。通过以下速率的这种氧化光学通过生产的ferroin衍生物在各种反应条件和颗粒衍生化，我们能够表明，fluxional配体壳分散，胶体纳米粒子提供了一个单独的和更容易的途径，电荷转移，其中的限速步骤是配体解离。由于这种配体壳层经常需要纳米颗粒的稳定性，这一观察结果具有显着的影响胶体纳米颗粒的稳定性。
Understanding charge transfer dynamics through the ligand shell of colloidal nanoparticles has been an important pursuit in solar energy conversion. While charge transport through ligand shells of nanoparticle films has been studied intensely in static dry and electrochemical systems, its influence on charge transfer kinetics in dispersed colloidal systems has received relatively less attention. This work reports the oxidation of amine passivated tungsten oxide nanoparticles by an organically soluble tris-(1,10-phenanthroline) iron(III) derivative. By following the rate of this oxidation optically via the production of the ferroin derivative under various reaction conditions and particle derivatizations, we are able to show that the fluxional ligand shells on dispersed, colloidal nanoparticles provide a separate and more facile pathway for charge transfer, in which the rate-limiting step for charge transfer is the ligand dissociation. Since such ligand shells are frequently required for nanoparticle stability, this observation has significant implications for colloidal nanoparticle photocatalysis.