关键词: 量子化学, 电化学表面增强拉曼光谱, 电荷转移态, 表面等离激元共振, 光电化学

Abstract:

At present photoelectrochemistry has received much concern back to nanostructures of noble metals from semiconductor electrodes. This is due to the surface plasmon resonance (SPR) effect of metallic nanostructures, which can effectively convert the far-field light to the near-field light and concentrate the photonic energy to the local surface area with high energy density. Thus, the different enhancement mechanisms, such as the local optical field enhancement, the formation of light generated hot carriers (hot electron-hole pairs), or the photothermal effect, have been proposed in literatures. On the basis of the SPR enhancement effect, the surface-enhanced Raman spectroscopy (SERS) can be used to characterize the surface species but also induce surface chemical reactions. This provides a new idea to study the synergic effect of light and electricity in electrochemical interfaces. The article first reviewed a brief history of photoelectrochemistry, and then summarized our work on the light splitting water to hydrogen molecules, the photo-driven surface catalytic coupling reactions of the p-aminothiophenol oxidation and the p-nitrothiophenol reduction in electrochemical interfaces. Finally, we presented a simple prospective on the relationship of the SPR and the hot electron-hole pairs to plasmon-enhanced photoelectrochemical reactions.

Key words: quantum chemistry, electrochemical surface-enhanced Raman spectroscopy, charge transfer state, surface plasmon resonance, photoelectrochemistry