Meyer Gerald J
Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA.
Inorg Chem. 2005 Oct 3;44(20):6852-64. doi: 10.1021/ic0505908.
Strategies toward the realization of molecular control of interfacial charge transfer at nanocrystalline semiconductor interfaces are described. Light excitation of coordination compounds, based on (dpi)6 transition metals, anchored to wide band-gap semiconductors, such as TiO2, can initiate electron-transfer processes that ultimately reduce the semiconductor. Such photoinduced charge-separation processes are a key step for solar energy conversion. The thermodynamics and kinetic rate constants for three different interfacial charge separation mechanisms are discussed. Tuning the energetic position of the semiconductor conduction band relative to the molecular sensitizer has provided new insights into interfacial charge transfer. Supramolecular compounds that efficiently absorb light, promote interfacial electron transfer, and feature additional functions such as intramolecular electron transfer when bound to semiconductor surfaces have also been studied. New approaches for enhancing charge-separation lifetimes for solar energy conversion are presented.
本文描述了实现纳米晶半导体界面电荷转移分子控制的策略。基于（dpi）6过渡金属的配位化合物光激发后，锚定在宽带隙半导体（如TiO2）上，可引发最终使半导体还原的电子转移过程。此类光致电荷分离过程是太阳能转换的关键步骤。讨论了三种不同界面电荷分离机制的热力学和动力学速率常数。调节半导体导带相对于分子敏化剂的能量位置，为界面电荷转移提供了新的见解。还研究了超分子化合物，其能有效吸收光、促进界面电子转移，并且在与半导体表面结合时具有诸如分子内电子转移等附加功能。提出了提高太阳能转换电荷分离寿命的新方法。
