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Plasmonic Hot Electron-Mediated Hydrodehalogenation Kinetics on Nanostructured Ag Electrodes
Journal of the American Chemical Society ( IF 15.0 ) Pub Date : 2020-09-17 , DOI: 10.1021/jacs.0c07027
Jia Liu 1 , Zhuan-Yun Cai 1 , Wei-Xin Sun 1 , Jia-Zheng Wang 1 , Xiao-Ru Shen 1 , Chao Zhan 1 , Rajkumar Devasenathipathy 1 , Jian-Zhang Zhou 1 , De-Yin Wu 1 , Bing-Wei Mao 1 , Zhong-Qun Tian 1
Affiliation  

An attractive field of plasmon-mediated chemical reaction (PMCR) is developing rapidly, but there is still incomplete under-standing of how to control the kinetics of such a reaction related to hot carriers. Here, we chose 8-bromoadenine (8BrAd) as a probe molecule of hot electrons to investigate the influence of the electrode potential, laser wavelength and power on the PMCR kinetics on silver nanoparticle-modified silver electrodes (Ag NPs@Ag). Plasmonic hot electron-mediated cleavage of the C-Br bond in 8BrAd has been investigated by combining in situ electrochemical surface-enhanced Raman spectroscopy (EC-SERS) and density functional theory (DFT) calculations. The experimental and theoretical results reveal that the energy position of plasmon relaxation-generated hot electrons can be modulated conveniently by applied potentials and laser light. This allows proposal of a mechanism of modulating the matching energy of the hot electron of plasmon relaxation to pro-mote the efficiency of PMCR in electrochemical interfaces. Our work will be helpful to design surface plasmon resonance (SPR) photoelectrochemical reactions on metal electrode surfaces of nanostructures with higher efficiency.

中文翻译:

纳米结构银电极上的等离子体热电子介导的加氢脱卤动力学

等离子体介导的化学反应 (PMCR) 的一个有吸引力的领域正在迅速发展,但对于如何控制与热载流子相关的这种反应的动力学仍然不完全了解。在这里,我们选择 8-溴腺嘌呤 (8BrAd) 作为热电子的探针分子来研究电极电位、激光波长和功率对银纳米颗粒修饰的银电极 (Ag NPs@Ag) 上 PMCR 动力学的影响。通过结合原位电化学表面增强拉曼光谱 (EC-SERS) 和密度泛函理论 (DFT) 计算,研究了 8BrAd 中 C-Br 键的等离子热电子介导裂解。实验和理论结果表明,等离子体弛豫产生的热电子的能量位置可以通过施加的电位和激光方便地进行调制。这允许提出一种调节等离子体弛豫热电子匹配能量的机制,以提高电化学界面中 PMCR 的效率。我们的工作将有助于以更高的效率设计纳米结构金属电极表面上的表面等离子体共振(SPR)光电化学反应。
更新日期:2020-09-17
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