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随着纳米科学的发展,人们再次关注到金属电极上的光电化学研究.这主要得益于币族金属纳米结构具有强的表面等离激元共振(SPR)效应,它能有效地将光从远场光转化为近场光,汇聚光能到金属表面区域,可以在表面产生强的光电场效应,或产生较长寿命的热电子-空穴载流子效应,或是更长时间尺度的热效应.因此,SPR效应不仅产生了表面增强拉曼散射(SERS)效应,用于表征吸附分子,而且可能诱发表面化学反应,为在电化学界面实现光与电协同调控化学反应提供新思路.本文首先回顾了金属电极上光电流理论的发展,然后总结了本研究组近年来将量子化学计算用于光电化学反应和SERS光谱研究的工作,并以在银金纳米结构电极上水合质子还原和芳香胺氧化为例,比较了热电子和热空穴参与光电化学反应的特点,揭示了SPR参与光电化学反应的本质.
With the development of nanoscience, attention has been paid again to the photoelectrochemical studies on metal electrodes, mainly due to the strong surface plasmon resonance (SPR) effect of the metal nanostructures, which can effectively separate light from Far-field light is converted into near-field light, which condenses the light energy into the metal surface region, which can produce strong photoelectric field effects on the surface or produce longer lifetime hot electron-hole carrier effects, or longer time scales Therefore, the SPR effect not only produces the surface enhanced Raman scattering (SERS) effect, which can be used to characterize the adsorbed molecules but also induce surface chemical reactions, providing new ideas for the coordinated control of chemical reactions by light and electricity at the electrochemical interface. Firstly, the development of the theory of photocurrent on metal electrodes is reviewed. Then, the research work of quantum chemistry calculations in the field of photoelectrochemical reaction and SERS spectroscopy has been summarized. In the meantime, the hydration of proton reduction and aromatic Amine oxidation was taken as an example to compare the characteristics of thermoelectrons and hot holes participating in the photoelectrochemical reaction and to reveal the nature of SPR participating in the photoelectrochemical reaction.