Plasmon-Driven Chemistry in Ferri-/Ferrocyanide Gold Nanoparticle Oligomers: A SERS Study
Plasmon-Driven Chemistry in Ferri-/Ferrocyanide Gold Nanoparticle Oligomers: A SERS Study
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DOI：
10.1021/jacs.0c05031
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发表时间：
2020-07-29
影响因子：
15
通讯作者：
Van Duyne, Richard P.
中科院分区：
文献类型：
--
作者：
Qi, Yue;Brasiliense, Vitor;Van Duyne, Richard P.
利用连续波泵浦-探测Sers研究了金纳米颗粒低聚物表面增强拉曼光谱（Sers）活性热点内亚铁氰化物离子的等离子体激元驱动化学。通过与溶液相正常的拉曼光谱比较，在532 nm光泵浦时观察到的特征光谱变化可以归因于发生在表面物种上的氧化过程，随后氧化的表面物种从金纳米颗粒解吸。询问在很宽的温度范围内的等离子体激元驱动的过程表明，这两个过程都不是纯粹由与光泵浦相关的热效应驱动的，这两个步骤的表观活化能估计基于半定量Sers分析。我们的观察确定了一个更详细的反应途径，这个经典的模型系统在相当简化的反应条件下，增加了目前的机制背景，为未来的等离子体激元驱动的化学研究和应用。
The plasmon-driven chemistry of ferri-/ferrocyanide ions inside surface-enhanced Raman spectroscopy (SERS) active hot spots associated with gold nanoparticle oligomers is studied with continuous wave (CW) pump-probe SERS. By comparing with solution-phase normal Raman spectra, the characteristic spectral variations observed upon 532 nm optical pumping can be attributed to an oxidation process that occurs on the surface species followed by desorption of the oxidized surface species from the gold nanoparticles. Interrogating the plasmon-driven processes over a wide range of temperatures reveals that neither process is purely driven by the thermal effects associated with the optical pumping, and the apparent activation energies of both steps are estimated based on semiquantitative SERS analysis. Our observation identifies a more detailed reaction pathway for this classic model system under considerably simplified reaction conditions, adding to the current mechanistic background for future plasmon-driven chemistry studies and applications.